Method for producing solid catalyst component for use in polymerization of olefin, catalyst for use in polymerization of olefin, and method for producing olefin polymer

ABSTRACT

A method for producing a solid catalyst component for olefin polymerization produces a novel solid catalyst component for olefin polymerization that achieves excellent olefin polymerization activity and activity with respect to hydrogen during polymerization, and can produce an olefin polymer that exhibits a high MFR, high stereoregularity, and excellent rigidity. The method includes a first step that brings a magnesium compound, a tetravalent titanium halide compound, and one or more first internal electron donor compounds selected from specific aromatic dicarboxylic diesters into contact with each other to effect a reaction, followed by washing, a second step that brings a tetravalent titanium halide compound and one or more second internal electron donor compounds into contact with a product obtained by the first step to effect a reaction, followed by washing, and a third step that brings one or more third internal electron donor compounds into contact with a product obtained by the second step to effect a reaction.

TECHNICAL FIELD

The invention relates to a method for producing a solid catalystcomponent for olefin polymerization, an olefin polymerization catalyst,and a method for producing an olefin polymer.

BACKGROUND ART

An olefin (e.g., propylene) has been polymerized using an olefinpolymerization catalyst. The resulting olefin polymer may be melted,molded using a molding machine, a stretching machine, or the like, andused for a variety of applications (e.g., automotive parts, homeappliance parts, containers, and films).

A solid catalyst component that includes magnesium, titanium, anelectron donor compound, and a halogen atom as essential components hasbeen known as a component of the olefin polymerization catalyst. Anumber of olefin polymerization catalysts have been proposed thatinclude the solid catalyst component, an organoaluminum compound, and anorganosilicon compound.

An olefin polymer has been desired that exhibits higher fluidity (meltflow rate (MFR)) when molded using a molding machine, a stretchingmachine, or the like.

The MFR of an olefin polymer mainly depends on the molecular weight ofthe olefin polymer, and an olefin polymer having a low molecular weighttends to have a high MFR. Therefore, the molecular weight of an olefinpolymer is normally reduced by adding a large amount of hydrogen duringpolymerization in order to obtain an olefin polymer having a high MFR.

In recent years, an olefin polymer that has a high MFR, highstereoregularity, a reduced thickness, and high physical strength (i.e.,excellent rigidity) has been desired for producing large home applianceparts and automotive parts (particularly a bumper).

In view of the above situation, the applicant of the present applicationproposed an olefin polymerization catalyst and an olefin polymerizationmethod using the olefin polymerization catalyst, the olefinpolymerization catalyst including a solid catalyst component, anorganoaluminum compound, and an organosilicon compound, the solidcatalyst component being obtained by bringing a magnesium compound, atetravalent titanium halide compound, a malonic diester (internalelectron donor compound), and a phthalic diester (internal electrondonor compound) into contact with each other (see Patent Document 1(JP-A-2004-107462)).

RELATED-ART DOCUMENT Patent Document

-   Patent Document 1: JP-A-2004-107462

SUMMARY OF THE INVENTION Technical Problem

The olefin polymerization catalyst disclosed in Patent Document 1exhibits excellent activity with respect to hydrogen as compared withknown polymerization catalysts, and an olefin polymer obtained using thesolid catalyst component disclosed in Patent Document 1 exhibits highfluidity (MFR) when melted, and is particularly useful when producing alarge molded article by injection molding or the like.

According to further studies conducted by the inventors of theinvention, however, it was found that it is necessary to increase theamount of each internal electron donor compound in order to obtain asolid catalyst component having the desired internal electron donorcompound content by simultaneously bringing two or more differentinternal electron donor compounds into contact with the other componentsto effect a reaction. As a result, a complex of excess internal electrondonor compound and the tetravalent titanium halide compound is easilyformed, and the polymerization activity and the stereoregularity of theresulting olefin polymer easily decrease when using the resulting solidcatalyst component as a component of an olefin polymerization catalyst.

Moreover, an olefin polymerization catalyst that can produce an olefinpolymer that exhibits higher rigidity has been desired.

When producing a large molded article by injection molding or the like,it may be necessary to use a copolymer of two or more α-olefins (e.g.,propylene and ethylene) instead of a homopolymer of a single olefin(e.g., propylene).

Therefore, a solid catalyst component for olefin polymerization and anolefin polymerization catalyst have been desired that exhibit excellentsustainability of polymerization activity, thus ensuring that thepolymerization activity can be maintained for a long time whenpolymerizing a single olefin (e.g., propylene), and can also bemaintained for a long time when subjecting two or more olefins tocopolymerization or multistep polymerization.

However, when propylene and another α-olefin are copolymerized by amultistep polymerization process using a known catalyst, for example,the polymerization activity significantly decreases duringcopolymerization in the second or subsequent step when a polymer havinghigh stereospecificity is produced by first-step propylenepolymerization (homopolymerization).

In view of the above situation, an object of the invention is to providea method for producing a novel solid catalyst component for olefinpolymerization that achieves excellent olefin polymerization activityand activity with respect to hydrogen during polymerization whenhomopolymerizing or copolymerizing an olefin, and can produce an olefinpolymer that exhibits a high MFR, high stereoregularity, and excellentrigidity while achieving high sustainability of polymerization activity,and also provide an olefin polymerization catalyst and a method forproducing an olefin polymer.

Solution to Problem

The inventors conducted extensive studies in order to achieve the aboveobject, and found that the above object can be achieved by producing asolid catalyst component for olefin polymerization by performing a firststep that brings a magnesium compound, a tetravalent titanium halidecompound, and one or more first internal electron donor compoundsselected from specific aromatic dicarboxylic diesters into contact witheach other to effect a reaction, followed by washing, a second step thatbrings a tetravalent titanium halide compound and one or more secondinternal electron donor compounds into contact with a product obtainedby the first step to effect a reaction, followed by washing, and a thirdstep that brings one or more third internal electron donor compoundsinto contact with a product obtained by the second step to effect areaction, preparing an olefin polymerization catalyst using the solidcatalyst component, and reacting an olefin using the olefinpolymerization catalyst. This finding has led to the completion of theinvention.

Specifically, several aspects of the invention provide the following.

(1) A method for producing a solid catalyst component for olefinpolymerization including:

a first step that brings a magnesium compound, a tetravalent titaniumhalide compound, and one or more first internal electron donor compoundsselected from aromatic dicarboxylic diesters represented by thefollowing general formula (I) into contact with each other to effect areaction, followed by washing;

a second step that brings a tetravalent titanium halide compound and oneor more second internal electron donor compounds into contact with aproduct obtained by the first step to effect a reaction, followed bywashing; and

a third step that brings one or more third internal electron donorcompounds into contact with a product obtained by the second step toeffect a reaction,

(R¹)_(j)C₆H_(4-j)(COOR²)(COOR³)  (I)

wherein R¹ is an alkyl group having 1 to 8 carbon atoms or a halogenatom, R² and R³ are an alkyl group having 1 to 12 carbon atoms, providedthat R² and R³ are either identical or different, and j, which is thenumber of substituents R¹, is 0, 1, or 2, provided that R¹ are eitheridentical or different when j is 2.(2) The method for producing a solid catalyst component for olefinpolymerization according to (1), wherein the second internal electrondonor compound is used so that the ratio “molar quantity of the secondinternal electron donor compound/molar quantity of the magnesiumcompound” is 0.001 to 10.(3) The method for producing a solid catalyst component for olefinpolymerization according to (1) or (2), wherein the third internalelectron donor compound is used so that the ratio “molar quantity of thethird internal electron donor compound/molar quantity of the magnesiumcompound” is 0.001 to 10.(4) The method for producing a solid catalyst component for olefinpolymerization according to any one of (1) to (3), wherein the firstinternal electron donor compound, the second internal electron donorcompound, and the third internal electron donor compound are used sothat the relationship “molar quantity of the first internal electrondonor compound>molar quantity of the second internal electron donorcompound≧molar quantity of the third internal electron donor compound”is satisfied.(5) The method for producing a solid catalyst component for olefinpolymerization according to any one of (1) to (4), wherein the thirdinternal electron donor compound is brought into contact with theproduct obtained by the second step in an inert organic solvent forwhich a tetravalent titanium halide compound content is controlled to 0to 5 mass %.(6) An olefin polymerization catalyst produced by bringing a solidcatalyst component for olefin polymerization obtained by the methodaccording to any one of (1) to (5), an organoaluminum compoundrepresented by the following general formula (II), and an externalelectron donor compound into contact with each other,

R⁴ _(p)AlQ_(3-p)  (II)

wherein R⁴ is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogenatom or a halogen atom, and p is a real number that satisfies 0<p≦3.(7) The olefin polymerization catalyst according to (6), wherein theexternal electron donor compound is one or more organosilicon compoundsselected from an organosilicon compound represented by the followinggeneral formula (III) and an organosilicon compound represented by thefollowing general formula (IV),

R⁵ _(q)Si(OR⁶)_(4-q)  (III)

wherein R⁵ is an alkyl group having 1 to 12 carbon atoms, a cycloalkylgroup having 3 to 12 carbon atoms, a phenyl group, a vinyl group, anallyl group, or an aralkyl group, provided that a plurality of R⁵ areeither identical or different when a plurality of R⁵ are present, R⁶ isan alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3to 6 carbon atoms, a phenyl group, a vinyl group, an allyl group, or anaralkyl group, provided that a plurality of R⁶ are either identical ordifferent when a plurality of R⁶ are present, and q is an integer from 0to 3,

(R⁷R⁸N)_(s)SiR⁹ _(4-s)  (IV)

wherein R⁷ and R⁸ are a hydrogen atom, a linear alkyl group having 1 to20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, avinyl group, an allyl group, an aralkyl group, a cycloalkyl group having3 to 20 carbon atoms, or an aryl group, provided that R⁷ and R⁸ areeither identical or different, and optionally bond to each other to forma ring, R⁹ is a linear alkyl group having 1 to 20 carbon atoms, abranched alkyl group having 3 to 20 carbon atoms, a vinyl group, anallyl group, an aralkyl group, a linear or branched alkoxy group having1 to 20 carbon atoms, a vinyloxy group, an allyloxy group, a cycloalkylgroup having 3 to 20 carbon atoms, an aryl group, or an aryloxy group,provided that a plurality of R⁹ are either identical or different when aplurality of R⁹ are present, and s is an integer from 1 to 3.(8) A method for producing an olefin polymer including polymerizing anolefin in the presence of the olefin polymerization catalyst accordingto (6) or (7).

Advantageous Effects of the Invention

The aspects of the invention thus provide a method for producing a novelsolid catalyst component for olefin polymerization that achievesexcellent olefin polymerization activity and activity with respect tohydrogen during polymerization when homopolymerizing or copolymerizingan olefin, and can produce an olefin polymer that exhibits a high MFR,high stereoregularity, and excellent rigidity while achieving highsustainability of polymerization activity, and also provide an olefinpolymerization catalyst and a method for producing an olefin polymer.

DESCRIPTION OF EMBODIMENTS

A method for producing a solid catalyst component for olefinpolymerization (hereinafter may be referred to as “production method”)according to one embodiment of the invention is described below.

The method for producing a solid catalyst component for olefinpolymerization according to one embodiment of the invention includes afirst step that brings a magnesium compound, a tetravalent titaniumhalide compound, and one or more first internal electron donor compoundsselected from aromatic dicarboxylic diesters represented by thefollowing general formula (I) into contact with each other to effect areaction, followed by washing, a second step that brings a tetravalenttitanium halide compound and one or more second internal electron donorcompounds into contact with a product obtained by the first step toeffect a reaction, followed by washing, and a third step that brings oneor more third internal electron donor compounds into contact with aproduct obtained by the second step to effect a reaction.

(R¹)_(j)C₆H_(4-j)(COOR²)(COOR³)  (I)

wherein R¹ is an alkyl group having 1 to 8 carbon atoms or a halogenatom, R² and R³ are an alkyl group having 1 to 12 carbon atoms, providedthat R² and R³ are either identical or different, and j, which is thenumber of substituents R¹, is 0, 1, or 2, provided that R¹ are eitheridentical or different when j is 2.

First Step

The magnesium compound used in connection with the method for producinga solid catalyst component for olefin polymerization according to oneembodiment of the invention may be one or more magnesium compoundsselected from a dialkoxymagnesium, a magnesium dihalide, analkoxymagnesium halide, and the like.

Among these magnesium compounds, a dialkoxymagnesium and a magnesiumdihalide are preferable. Specific examples of the dialkoxymagnesium andthe magnesium dihalide include dimethoxymagnesium, diethoxymagnesium,dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium,ethoxypropoxymagnesium, butoxyethoxymagnesium, magnesium dichloride,magnesium dibromide, magnesium diiodide, and the like. Among these,diethoxymagnesium and magnesium dichloride are particularly preferable.

The dialkoxymagnesium may be a dialkoxymagnesium that is obtained byreacting magnesium metal with an alcohol in the presence of a halogen, ahalogen-containing metal compound, or the like.

It is preferable to use a granular or powdery dialkoxymagnesium whenimplementing the method for producing a solid catalyst component forolefin polymerization according to one embodiment of the invention. Thedialkoxymagnesium may have an indefinite shape or a spherical shape.

When a spherical dialkoxymagnesium is used, the resulting polymer powderhas a better (more spherical) particle shape and a narrower particlesize distribution. This improves the handling capability of the polymerpowder produced during polymerization, and eliminates occurrence of aproblem (e.g., clogging) due to a fine powder included in the polymerpowder.

The spherical dialkoxymagnesium need not necessarily have a perfectspherical shape, but may have an elliptical shape or a potato-likeshape. It is preferable that the dialkoxymagnesium particles have asphericity of 3 or less, more preferably 1 to 2, and still morepreferably 1 to 1.5.

Note that the term “sphericity” used herein in connection with thedialkoxymagnesium particles refers to a value obtained by photographing500 or more dialkoxymagnesium particles using a scanning electronmicroscope, processing the photographed particles using image analysissoftware to determine the area S and the circumferential length L ofeach particle, calculating the sphericity of each dialkoxymagnesiumparticle using the following expression, and calculating the arithmeticmean value. The sphericity is close to 1 when the shape of the particleis close to a true circle.

Sphericity of each dialkoxymagnesium particle=4π×S÷L ²

The average particle size D50 (i.e., the particle size at 50% in thecumulative volume particle size distribution) of the dialkoxymagnesiummeasured using a laser diffraction/scattering particle size distributionanalyzer is preferably 1 to 200 μm, and more preferably 5 to 150 μm.

The average particle size of the spherical dialkoxymagnesium ispreferably 1 to 100 μm, more preferably 5 to 60 and still morepreferably 10 to 50 μm.

It is preferable that the dialkoxymagnesium have a narrow particle sizedistribution, and have a low fine particle content and a low coarseparticle content.

Specifically, it is preferable that the dialkoxymagnesium have a contentof particles having a particle size (measured using a laserdiffraction/scattering particle size distribution analyzer) of 5 μm orless of 20% or less, and more preferably 10% or less. It is preferablethat the dialkoxymagnesium have a content of particles having a particlesize (measured using a laser diffraction/scattering particle sizedistribution analyzer) of 100 μm or more of 10% or less, and morepreferably 5% or less.

The particle size distribution ln(D90/D10) (where, D90 is the particlesize at 90% in the cumulative volume particle size distribution, and D10is the particle size at 10% in the cumulative volume particle sizedistribution) of the dialkoxymagnesium is preferably 3 or less, and morepreferably 2 or less.

The spherical dialkoxymagnesium may be produced using the methoddisclosed in JP-A-58-41832, JP-A-62-51633, JP-A-3-74341, JP-A-4-368391,JP-A-8-73388, or the like.

When implementing the method for producing a solid catalyst componentfor olefin polymerization according to one embodiment of the invention,it is preferable that the magnesium compound be used in the form of asolution or a suspension when subjected to the reaction. When themagnesium compound is used in the form of a solution or a suspension,the reaction proceeds advantageously.

When the magnesium compound is solid, the magnesium compound may bedissolved in a solvent that can dissolve the magnesium compound toprepare a magnesium compound solution, or may be suspended in a solventthat cannot dissolve the magnesium compound to prepare a magnesiumcompound suspension.

When the magnesium compound is liquid, the magnesium compound may beused directly, or may be dissolved in a solvent that can dissolve themagnesium compound to prepare a magnesium compound solution.

Examples of a compound that can dissolve the solid magnesium compoundinclude at least one compound selected from the group consisting ofalcohols, ethers, and esters.

Specific examples of the compound that can dissolve the solid magnesiumcompound include alcohols having 1 to 18 carbon atoms, such as methanol,ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol,dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethylalcohol, cumyl alcohol, isopropyl alcohol, isopropylbenzyl alcohol, andethylene glycol, halogen-containing alcohols having 1 to 18 carbonatoms, such as trichloromethanol, trichloroethanol, andtrichlorohexanol, ethers having 2 to 20 carbon atoms, such as methylether, ethyl ether, isopropyl ether, butyl ether, amyl ether,tetrahydrofuran, ethyl benzyl ether, dibutyl ether, anisole, anddiphenyl ether, metal acid esters such as tetraethoxytitanium,tetra-n-propoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium,tetrahexoxytitanium, tetrabutoxyzirconium, and tetraethoxyzirconium, andthe like.

Among these, alcohols such as ethanol, propanol, butanol, and2-ethylhexanol are preferable, and 2-ethylhexanol is particularlypreferable.

Examples of a compound that cannot dissolve the solid magnesium compoundinclude one or more compounds selected from a saturated hydrocarbonsolvent and an unsaturated hydrocarbon solvent that do not dissolve amagnesium compound.

The saturated hydrocarbon solvent and the unsaturated hydrocarbonsolvent are safe, and have high industrial versatility. Examples of thesaturated hydrocarbon solvent and the unsaturated hydrocarbon solventinclude linear or branched aliphatic hydrocarbon compounds having aboiling point of 50 to 200° C., such as hexane, heptane, decane, andmethylheptane, alicyclic hydrocarbon compounds having a boiling point of50 to 200° C., such as cyclohexane, ethylcyclohexane, anddecahydronaphthalene, and aromatic hydrocarbon compounds having aboiling point of 50 to 200° C., such as toluene, xylene, andethylbenzene. Among these, linear aliphatic hydrocarbon compounds havinga boiling point of 50 to 200° C., such as hexane, heptane, and decane,and aromatic hydrocarbon compounds having a boiling point of 50 to 200°C., such as toluene, xylene, and ethylbenzene, are preferable.

The tetravalent titanium halide compound used in the first step includedin the method for producing a solid catalyst component for olefinpolymerization according to one embodiment of the invention is notparticularly limited. It is preferable that the tetravalent titaniumhalide compound be one or more compounds selected from a titanium halideand an alkoxytitanium halide represented by the following generalformula (V).

Ti(OR¹⁰)_(r)X_(4-r)  (V)

wherein R¹⁰ is an alkyl group having 1 to 4 carbon atoms, X is a halogenatom (e.g., chlorine atom, bromine atom, or iodine atom), and r is aninteger from 0 to 3.

Examples of the titanium halide include titanium tetrahalides such astitanium tetrachloride, titanium tetrabromide, and titanium tetraiodide.

Examples of the alkoxytitanium halide include methoxytitaniumtrichloride, ethoxytitanium trichloride, propoxytitanium trichloride,n-butoxytitanium trichloride, dimethoxytitanium dichloride,diethoxytitanium dichloride, dipropoxytitanium dichloride,di-n-butoxytitanium dichloride, trimethoxytitanium chloride,triethoxytitanium chloride, tripropoxytitanium chloride,tri-n-butoxytitanium chloride, and the like.

Among these, titanium tetrahalides are preferable, and titaniumtetrachloride is more preferable.

These titanium compounds may be used either alone or in combination.

One or more first internal electron donor compounds selected fromaromatic dicarboxylic diesters (phthalic diester or substituted phthalicdiester) represented by the following general formula (I) are used inthe first step included in the method for producing a solid catalystcomponent for olefin polymerization according to one embodiment of theinvention.

(R¹)_(j)C₆H_(4-j)(COOR²)(COOR³)  (I)

wherein R¹ is an alkyl group having 1 to 8 carbon atoms or a halogenatom, R² and R³ are an alkyl group having 1 to 12 carbon atoms, providedthat R² and R³ are either identical or different, and j, which is thenumber of substituents R¹, is 0, 1, or 2, provided that R¹ are eitheridentical or different when j is 2.

R¹ in the aromatic dicarboxylic diester represented by the generalformula (I) is a halogen atom or an alkyl group having 1 to 8 carbonatoms.

Examples of the halogen atom represented by R¹ include one or more atomsselected from a fluorine atom, a chlorine atom, a bromine atom, and aniodine atom.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R¹include one or more groups selected from a methyl group, an ethyl group,a n-propyl group, an isopropyl group, a n-butyl group, an isobutylgroup, a t-butyl group, a n-pentyl group, an isopentyl group, aneopentyl group, a n-hexyl group, an isohexyl group, a 2,2-dimethylbutylgroup, a 2,2-dimethylpentyl group, an isooctyl group, and a2,2-dimethylhexyl group.

R¹ is preferably a methyl group, a bromine atom, or a fluorine atom, andmore preferably a methyl group or a bromine atom.

R² and R³ in the aromatic dicarboxylic diester represented by thegeneral formula (I) are an alkyl group having 1 to 12 carbon atoms,provided that R² and R³ are either identical or different.

Examples of the alkyl group having 1 to 12 carbon atoms include a methylgroup, an ethyl group, a n-propyl group, an isopropyl group, a n-butylgroup, an isobutyl group, a t-butyl group, a n-pentyl group, anisopentyl group, a neopentyl group, a n-hexyl group, an isohexyl group,a 2,2-dimethylbutyl group, a 2,2-dimethylpentyl group, an isooctylgroup, a 2,2-dimethylhexyl group, a n-nonyl group, an isononyl group, an-decyl group, an isodecyl group, and a n-dodecyl group. Among these, anethyl group, a n-propyl group, a n-butyl group, an isobutyl group, at-butyl group, a neopentyl group, an isohexyl group, and an isooctylgroup (particularly an ethyl group, a n-propyl group, a n-butyl group,an isobutyl group, and a neopentyl group) are preferable.

j (i.e., the number of substituents R¹) in the aromatic dicarboxylicdiester represented by the general formula (I) is 0, 1, or 2, providedthat R′ (two R¹) are either identical or different when j is 2.

The compound represented by the general formula (I) is a phthalicdiester when j is 0, and is a substituted phthalic diester when j is 1or 2.

When j is 1, it is preferable that R¹ in the aromatic dicarboxylicdiester represented by the general formula (I) substitute the hydrogenatom at position 3, 4, or 5 of the benzene ring.

When j is 2, it is preferable that R¹ in the aromatic dicarboxylicdiester represented by the general formula (I) substitute the hydrogenatom at position 4 or 5 of the benzene ring.

Specific examples of the aromatic dicarboxylic diester represented bythe general formula (I) include phthalic diesters such as dimethylphthalate, diethyl phthalate, di-n-propyl phthalate, diisopropylphthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-pentylphthalate, diisopentyl phthalate, dineopentyl phthalate, di-n-hexylphthalate, dithexyl phthalate, methylethyl phthalate, (ethyl)n-propylphthalate, ethylisopropyl phthalate, (ethyl)n-butyl phthalate,ethylisobutyl phthalate, (ethyl)n-pentyl phthalate, ethylisopentylphthalate, ethylneopentyl phthalate, and (ethyl)n-hexyl phthalate,halogen-substituted phthalic diesters such as diethyl 4-chlorophthalate,di-n-propyl 4-chlorophthalate, diisopropyl 4-chlorophthalate, di-n-butyl4-chlorophthalate, diisobutyl 4-chlorophthalate, diethyl4-bromophthalate, di-n-propyl 4-bromophthalate, diisopropyl4-bromophthalate, di-n-butyl 4-bromophthalate, and diisobutyl4-bromophthalate, alkyl-substituted phthalic diesters such as diethyl4-methylphthalate, di-n-propyl 4-methylphthalate, diisopropyl4-methylphthalate, di-n-butyl 4-methylphthalate, and diisobutyl4-methylphthalate, and the like.

Among these, diethyl phthalate, di-n-propyl phthalate, di-n-butylphthalate, diisobutyl phthalate, di-n-pentyl phthalate, diisopentylphthalate, dineopentyl phthalate, di-n-hexyl phthalate, (ethyl)n-propylphthalate, ethylisopropyl phthalate, (ethyl)n-butyl phthalate,ethylisobutyl phthalate, diethyl 4-methylphthalate, di-n-propyl4-methylphthalate, diisobutyl 4-methylphthalate, diisobutyl4-bromophthalate, diisopentyl 4-bromophthalate, dineopentyl4-bromophthalate, and the like are preferable, and diethyl phthalate,di-n-propyl phthalate, di-n-butyl phthalate, diisobutyl phthalate,(ethyl)n-propyl phthalate, ethylisopropyl phthalate, (ethyl)n-butylphthalate, ethylisobutyl phthalate, diethyl 4-methylphthalate,di-n-propyl 4-methylphthalate, diisobutyl 4-methylphthalate, diisobutyl4-bromophthalate, diisopentyl 4-bromophthalate, and dineopentyl4-bromophthalate are more preferable.

In the first step included in the method for producing a solid catalystcomponent for olefin polymerization according to one embodiment of theinvention, the magnesium compound, the tetravalent titanium halidecompound, and one or more first internal electron donor compoundsselected from the aromatic dicarboxylic diester represented by thegeneral formula (I) are brought into contact with each other to effect areaction, followed by washing.

In the first step, it is preferable to bring the magnesium compound, thetetravalent titanium halide compound, and the aromatic dicarboxylicdiester represented by the general formula (I) into contact with eachother in the presence of an inert organic solvent to effect a reaction.

It is preferable to use a compound that is liquid at room temperature(20° C.) and has a boiling point of 50 to 150° C. as the inert organicsolvent. It is more preferable to use an aromatic hydrocarbon compoundor a saturated hydrocarbon compound that is liquid at room temperatureand has a boiling point of 50 to 150° C. as the inert organic solvent.

Examples of the inert organic solvent include one or more compoundsselected from linear aliphatic hydrocarbon compounds such as hexane,heptane, and decane, branched aliphatic hydrocarbon compounds such asmethylheptane, alicyclic hydrocarbon compounds such as cyclohexane,methylcyclohexane, and ethylcyclohexane, aromatic hydrocarbon compoundssuch as toluene, xylene, and ethylbenzene, and the like.

Among these, aromatic hydrocarbon compounds that are liquid at roomtemperature and have a boiling point of 50 to 150° C. are preferablesince the activity of the resulting solid catalyst component and thestereoregularity of the resulting polymer can be improved.

In the first step included in the method for producing a solid catalystcomponent for olefin polymerization according to one embodiment of theinvention, the magnesium compound, the tetravalent titanium halidecompound, and the aromatic dicarboxylic diester represented by thegeneral formula (I) may be brought into contact with each other byappropriately mixing the magnesium compound, the tetravalent titaniumhalide compound, and the aromatic dicarboxylic diester in the presenceof the inert organic solvent.

In the first step, the magnesium compound, the tetravalent titaniumhalide compound, and the aromatic dicarboxylic diester represented bythe general formula (I) are brought into contact with each other toeffect a reaction.

The reaction temperature is preferably 0 to 130° C., more preferably 40to 130° C., still more preferably 30 to 120° C., and yet more preferably80 to 120° C. The reaction time is preferably 1 minute or more, morepreferably 10 minutes or more, still more preferably 30 minutes to 6hours, still more preferably 30 minutes to 5 hours, and yet morepreferably 1 to 4 hours.

In the first step, the components may be subjected to a low-temperatureaging treatment before effecting the reaction.

The low-temperature aging treatment brings the components into contactwith each other (preliminary reaction) at a temperature lower than thereaction temperature. The low-temperature aging temperature ispreferably −20 to 70° C., more preferably −10 to 60° C., and still morepreferably −10 to 30° C. The low-temperature aging time is preferably 1minute to 6 hours, more preferably 5 minutes to 4 hours, and still morepreferably 30 minutes to 3 hours.

When bringing the magnesium compound, the tetravalent titanium halidecompound, and the aromatic dicarboxylic diester represented by thegeneral formula (I) into contact with each other in the first step toeffect a reaction, the tetravalent titanium halide compound ispreferably used in an amount of 0.5 to 100 mol, more preferably 1 to 50mol, and still more preferably 1 to 10 mol, based on 1 mol of themagnesium compound.

When bringing the magnesium compound, the tetravalent titanium halidecompound, and the aromatic dicarboxylic diester represented by thegeneral formula (I) into contact with each other in the first step toeffect a reaction, the aromatic dicarboxylic diester represented by thegeneral formula (I) is preferably used in an amount of 0.01 to 10 mol,more preferably 0.01 to 1 mol, and still more preferably 0.02 to 0.6mol, based on 1 mol of the magnesium compound.

When using the inert organic solvent in the first step, the inertorganic solvent is preferably used in an amount of 0.001 to 500 mol,more preferably 0.5 to 100 mol, and still more preferably 1.0 to 20 mol,based on 1 mol of the magnesium compound.

In the first step, it is preferable to bring the components into contactwith each other with stirring in a vessel equipped with a stirrer thatcontains an inert gas atmosphere from which water and the like have beenremoved.

After completion of the reaction, it is preferable to wash the reactionproduct after allowing the reaction mixture to stand, appropriatelyremoving the supernatant liquid to achieve a wet state (slurry state),and optionally drying the reaction mixture by hot-air drying or thelike.

After completion of the reaction, the reaction mixture is allowed tostand, and the reaction product is washed after appropriately removingthe supernatant liquid.

The reaction product is normally washed using a washing agent.

Examples of the washing agent include those mentioned above inconnection with the inert organic solvent that is appropriately used inthe first step. The washing agent is preferably one or more compoundsselected from linear aliphatic hydrocarbon compounds that are liquid atroom temperature and have a boiling point of 50 to 150° C., such ashexane, heptane, and decane, alicyclic hydrocarbon compounds that areliquid at room temperature and have a boiling point of 50 to 150° C.,such as methylcyclohexane and ethylcyclohexane, aromatic hydrocarboncompounds that are liquid at room temperature and have a boiling pointof 50 to 150° C., such as toluene, xylene, ethylbenzene, ando-dichlorobenzene, and the like.

It is possible to easily remove (dissolve) by-products and impuritiesfrom the reaction product by utilizing the washing agent.

In the first step included in the method for producing a solid catalystcomponent for olefin polymerization according to one embodiment of theinvention, the reaction product is preferably washed at 0 to 120° C.,more preferably 0 to 110° C., more preferably 30 to 110° C., still morepreferably 50 to 110° C., and yet more preferably 50 to 100° C.

When implementing the method for producing a solid catalyst componentfor olefin polymerization according to one embodiment of the invention,it is preferable to wash the reaction product by adding the desiredamount of washing agent to the reaction product, stirring the mixture,and removing the liquid phase using a filtration method or a decantationmethod.

When washing the reaction product two or more times (as describedlater), the subsequent reaction (i.e., the reaction effected in thesubsequent step) may be effected without removing the washing agent thatwas added last to the reaction product.

It is preferable to use the washing agent in the first step in an amountof 1 to 500 mL, more preferably 3 to 200 mL, and still more preferably 5to 100 mL, per gram of the reaction product.

The reaction product may be washed two or more times. The reactionproduct is preferably washed 1 to 20 times, more preferably 2 to 15times, and still more preferably 2 to 10 times.

When washing the reaction product two or more times, it is preferable touse the washing agent in an amount within the above range each time thereaction product is washed.

According to the method for producing a solid catalyst component forolefin polymerization according to one embodiment of the invention, itis possible to remove unreacted raw material components, reactionby-products (e.g., alkoxytitanium halide and titaniumtetrachloride-carboxylic acid complex), and impurities that remain inthe reaction product by washing the reaction product in the first stepafter bringing the components into contact with each other to effect areaction.

In the first step included in the method for producing a solid catalystcomponent for olefin polymerization according to one embodiment of theinvention, a post-treatment may be appropriately performed after washingthe reaction product. Specifically, the reaction product subjected tothe post-treatment in the first step may be subjected to the second step(described below). Note that it is preferable to subject the reactionproduct directly to the second step without subjecting the reactionproduct to the post-treatment and the like.

After completion of the reaction, the suspension obtained by washing maybe allowed to stand, and the supernatant liquid may be removed toachieve a wet state (slurry state). The reaction mixture may optionallybe dried by hot-air drying or the like. The suspension obtained bywashing may be subjected directly to the second step. When subjectingthe suspension obtained by washing directly to the second step, thedrying treatment can be omitted, and it is unnecessary to add an inertorganic solvent in the second step.

Second Step

In the second step included in the method for producing a solid catalystcomponent for olefin polymerization according to one embodiment of theinvention, the tetravalent titanium halide compound and one or moresecond internal electron donor compounds are brought into contact withthe product obtained by the first step to effect a reaction, followed bywashing.

Examples of the tetravalent titanium halide compound used in the secondstep included in the method for producing a solid catalyst component forolefin polymerization according to one embodiment of the inventioninclude those mentioned above in connection with the tetravalenttitanium halide compound used in the first step.

The second internal electron donor compound used in the second stepincluded in the method for producing a solid catalyst component forolefin polymerization according to one embodiment of the invention ispreferably one or more compounds selected from organic compounds thatinclude two or more electron donor sites and do not include silicon.Examples of the electron donor site include a hydroxyl group (—OH), acarbonyl group (>C═O), an ether linkage (—OR), an amino group (—NH₂,—NHR, or —NHRR′), a cyano group (—CN), an isocyanate group (—N═C═O), andan amide linkage (—C(═O)NH— or —C(═O)NR—). A carbonyl group (>C═O) maybe those included in an aldehyde group (—C(═O)H), a carboxyl group(—C(═O)OH), a keto group (—C(═O)R), a carbonate group (—O—C(═O)O—), anester linkage (—C(═O)O—), an urethane linkage (—NH—C(═O)O—), and thelike. Among these, esters such as a polycarboxylic ester, and ethercompounds such as a diether and an ether carbonate are preferable. Theseinternal electron donor compounds may be used either alone or incombination.

Examples of the polycarboxylic ester that may be used in the second stepinclude carboxylic diesters, and substituted carboxylic diesters inwhich some of the hydrogen atoms bonded to the carbon atom that formsthe molecular skeleton are substituted with a substituent.

Examples of the carboxylic diesters include aromatic dicarboxylicdiesters such as a phthalic diester and an isophthalic diester,aliphatic dicarboxylic diesters such as a succinic diester, a maleicdiester, a malonic diester, and a glutaric diester, alicyclicdicarboxylic diesters such as a cycloalkanedicarboxylic diester and acycloalkenedicarboxylic diester, and the like.

Examples of the substituted carboxylic diesters includehalogen-substituted carboxylic diesters in which a hydrogen atom issubstituted with a halogen atom such as a fluorine atom, a chlorineatom, a bromine atom, or an iodine atom, alkyl-substituted carboxylicdiesters in which a hydrogen atom is substituted with an alkyl grouphaving 1 to 8 carbon atoms, alkyl halide-substituted carboxylic diestersin which a hydrogen atom is substituted with a halogen atom and an alkylgroup having 1 to 8 carbon atoms, and the like.

Specific examples of the substituted carboxylic diesters include asubstituted cycloalkanedicarboxylic diester in which some of thehydrogen atoms of the cycloalkyl group are substituted with an alkylgroup or the like, a substituted malonic diester, an alkyl-substitutedmaleic diester, and the like.

Examples of the aromatic dicarboxylic diester that may be used as thesecond internal electron donor compound include those mentioned above inconnection with the aromatic dicarboxylic diester represented by thegeneral formula (I).

Examples of the succinic diester that may be used as the second internalelectron donor compound include diethyl succinate, dibutyl succinate,diethyl methylsuccinate, diethyl 2,3-diisopropylsuccinate, and the like.Among these, diethyl succinate and diethyl 2,3-diisopropylsuccinate arepreferable.

Examples of the maleic diester that may be used as the second internalelectron donor compound include diethyl maleate, di-n-propyl maleate,diisopropyl maleate, di-n-butyl maleate, diisobutyl maleate, di-n-pentylmaleate, dineopentyl maleate, dihexyl maleate, dioctyl maleate, and thelike. Among these, diethyl maleate, di-n-butyl maleate, and diisobutylmaleate are preferable.

Examples of the alkyl-substituted maleic diester that may be used as thesecond internal electron donor compound include diethylisopropylbromomaleate, diethyl butylbromomaleate, diethylisobutylbromomaleate, diethyl diisopropylmaleate, diethyldibutylmaleate, diethyl diisobutylmaleate, diethyl diisopentylmaleate,diethyl isopropylisobutylmaleate, dimethyl isopropylisopentylmaleate,diethyl(3-chloro-n-propyl)maleate, diethyl bis(3-bromo-n-propyl)maleate,dibutyl dimethylmaleate, dibutyl diethylmaleate, and the like. Amongthese, dibutyl dimethylmaleate, dibutyl diethylmaleate, and diethyldiisobutylmaleate are preferable.

Examples of the malonic diester that may be used as the second internalelectron donor compound include dimethyl malonate, diethyl malonate,di-n-propyl malonate, diisopropyl malonate, di-n-butyl malonate,diisobutyl malonate, dineopentyl malonate, and the like. Among these,dimethyl malonate, diethyl malonate, and diisobutyl malonate arepreferable.

A substituted malonic diester is preferable as the second internalelectron donor compound.

Examples of the substituted malonic diester that may be used as thesecond internal electron donor compound include an alkyl-substitutedmalonic diester, a halogen-substituted malonic diester, an alkylhalide-substituted malonic diester, and the like. Among these, analkyl-substituted malonic diester and a halogen-substituted malonicdiester are preferable, and an alkyl-substituted malonic diester is morepreferable.

Examples of the alkyl-substituted malonic diester includemonoalkylmalonic diesters such as dimethyl methylmalonate, diethylmethylmalonate, dipropyl methylmalonate, diisopropyl methylmalonate,dibutyl methylmalonate, diisobutyl methylmalonate, dineopentylmethylmalonate, dimethyl ethylmalonate, diethyl ethylmalonate, dipropylethylmalonate, diisopropyl ethylmalonate, dibutyl ethylmalonate,diisobutyl ethylmalonate, dineopentyl ethylmalonate, dimethylpropylmalonate, diethyl isopropylmalonate, dipropyl isopropylmalonate,diisopropyl isopropylmalonate, dibutyl isopropylmalonate, diisobutylisopropylmalonate, dineopentyl isopropylmalonate, dimethylisobutylmalonate, diethyl isobutylmalonate, dipropyl isobutylmalonate,diisopropyl isobutylmalonate, dibutyl isobutylmalonate, diisobutylisobutylmalonate, dineopentyl isobutylmalonate, dimethylisopentylmalonate, diethyl isopentylmalonate, dipropylisopentylmalonate, diisopropyl isopentylmalonate, dibutylisopentylmalonate, diisobutyl isopentylmalonate, and dineopentylisopentylmalonate, dialkylmalonic diesters such as dimethylcyclopentylmethylmalonate, diethyl cyclopentylmethylmalonate, dipropylcyclopentylmethylmalonate, diisopropyl cyclopentylmethylmalonate,dibutyl cyclopentylmethylmalonate, diisobutyl cyclopentylmethylmalonate,dineopentyl cyclopentylmethylmalonate, dimethylcyclopentylethylmalonate, diethyl cyclopentylethylmalonate, dipropylcyclopentylethylmalonate, diisopropyl cyclopentylethylmalonate, dibutylcyclopentylethylmalonate, diisobutyl cyclopentylethylmalonate,dineopentyl cyclopentylethylmalonate, dimethylcyclopentylpropylmalonate, diethyl cyclopentylisopropylmalonate,dipropyl cyclopentylisopropylmalonate, diisopropylcyclopentylisopropylmalonate, dibutyl cyclopentylisopropylmalonate,diisobutyl cyclopentylisopropylmalonate, dineopentylcyclopentylisopropylmalonate, dimethyl cyclopentylisobutylmalonate,diethyl cyclopentylisobutylmalonate, dipropylcyclopentylisobutylmalonate, diisopropyl cyclopentylisobutylmalonate,dibutyl cyclopentylisobutylmalonate, diisobutylcyclopentylisobutylmalonate, dineopentyl cyclopentylisobutylmalonate,dimethyl cyclopentylisopentylmalonate, diethylcyclopentylisopentylmalonate, dipropyl cyclopentylisopentylmalonate,diisopropyl cyclopentylisopentylmalonate, dibutylcyclopentylisopentylmalonate, diisobutyl cyclopentylisopentylmalonate,dineopentyl cyclopentylisopentylmalonate, dimethylcyclohexylmethylmalonate, diethyl cyclohexylmethylmalonate, dipropylcyclohexylmethylmalonate, diisopropyl cyclohexylmethylmalonate, dibutylcyclohexylmethylmalonate, diisobutyl cyclohexylmethylmalonate,dineopentyl cyclohexylmethylmalonate, dimethyl cyclohexylethylmalonate,diethyl cyclohexylethylmalonate, dipropyl cyclohexylethylmalonate,diisopropyl cyclohexylethylmalonate, dibutyl cyclohexylethylmalonate,diisobutyl cyclohexylethylmalonate, dineopentyl cyclohexylethylmalonate,dimethyl cyclohexylpropylmalonate, diethyl cyclohexylisopropylmalonate,dipropyl cyclohexylisopropylmalonate, diisopropylcyclohexylisopropylmalonate, dibutyl cyclohexylisopropylmalonate,diisobutyl cyclohexylisopropylmalonate, dineopentylcyclohexylisopropylmalonate, dimethyl cyclohexylisobytylmalonate,diethyl isobutylmalonate, dipropyl cyclohexylisobutylmalonate,diisopropyl cyclohexylisobutylmalonate, dibutylcyclohexylisobutylmalonate, diisobutyl cyclohexylisobutylmalonate,dineopentyl cyclohexylisobutylmalonate, dimethylcyclohexylisopentylmalonate, diethyl cyclohexylisopentylmalonate,dipropyl cyclohexylisopentylmalonate, diisopropylcyclohexylisopentylmalonate, dibutyl cyclohexylisopentylmalonate,diisobutyl cyclohexylisopentylmalonate, dineopentylcyclohexylisopentylmalonate, dimethyl phenylmethylmalonate, diethylphenylmethylmalonate, dipropyl phenylmethylmalonate, diisopropylphenylmethylmalonate, dibutyl phenylmethylmalonate, diisobutylphenylmethylmalonate, dineopentyl phenylmethylmalonate, dimethylphenylethylmalonate, diethyl phenylethylmalonate, dipropylphenylethylmalonate, diisopropyl phenylethylmalonate, dibutylphenylethylmalonate, diisobutyl phenylethylmalonate, dineopentylphenylethylmalonate, dimethyl phenylpropylmalonate, diethylphenylisopropylmalonate, dipropyl phenylisopropylmalonate, diisopropylphenylisopropylmalonate, dibutyl phenylisopropylmalonate, diisobutylphenylisopropylmalonate, dineopentyl phenylisopropylmalonate, dimethylphenylisobutylmalonate, diethyl phenylisobutylmalonate, dipropylphenylisobutylmalonate, diisopropyl phenylisobutylmalonate, dibutylphenylisobutylmalonate, diisobutyl phenylisobutylmalonate, dineopentylphenylisobutylmalonate, dimethyl phenylisopentylmalonate, diethylphenylisopentylmalonate, dipropyl phenylisopentylmalonate, diisopropylphenylisopentylmalonate, dibutyl phenylisopentylmalonate, diisobutylphenylisopentylmalonate, dineopentyl phenylisopentylmalonate, dimethyldiisopropylmalonate, diethyl diisopropylmalonate, dipropyldiisopropylmalonate, diisopropyl diisopropylmalonate, dibutyldiisopropylmalonate, diisobutyl diisopropylmalonate, dineopentyldiisopropylmalonate, dimethyl diisobutylmalonate, diethyldiisobutylmalonate, dipropyl diisobutylmalonate, diisopropyldiisobutylmalonate, dibutyl diisobutylmalonate, diisobutyldiisobutylmalonate, dineopentyl diisobutylmalonate, dimethyldiisopentylmalonate, diethyl diisopentylmalonate, dipropyldiisopentylmalonate, diisopropyl diisopentylmalonate, dibutyldiisopentylmalonate, diisobutyl diisopentylmalonate, dineopentyldiisopentylmalonate, dimethyl isopropylisobutylmalonate, diethylisopropylisobutylmalonate, dipropyl isopropylisobutylmalonate,diisopropyl isopropylisobutylmalonate, dibutylisopropylisobutylmalonate, diisobutyl isopropylisobutylmalonate,dineopentyl isopropylisobutylmalonate, dimethylisopropylisopentylmalonate, diethyl isopropylisopentylmalonate, dipropylisopropylisopentylmalonate, diisopropyl isopropylisopentylmalonate,dibutyl isopropylisopentylmalonate, diisobutylisopropylisopentylmalonate, and dineopentyl isopropylisopentylmalonate,alkylidenemalonic diesters such as dimethyl propylidenemalonate, diethylpropylidenemalonate, di-n-propyl propylidenemalonate, diisobutylpropylidenemalonate, di-n-butyl propylidenemalonate, dimethylbutylidenemalonate, diethyl butylidenemalonate, di-n-propylbutylidenemalonate, diisobutyl butylidenemalonate, di-n-butylbutylidenemalonate, dimethyl pentylidenemalonate, diethylpentylidenemalonate, di-n-propyl pentylidenemalonate, diisobutylpentylidenemalonate, di-n-butyl pentylidenemalonate, dimethylhexylidenemalonate, diethyl hexylidenemalonate, di-n-propylhexylidenemalonate, diisobutyl hexylidenemalonate, di-n-butylhexylidenemalonate, dimethyl(2-methylpropylidene)malonate,diethyl(2-methylpropylidene)malonate,di-n-propyl(2-methylpropylidene)malonate,diisobutyl(2-methylpropylidene)malonate,di-n-butyl(2-methylpropylidene)malonate,diethyl(2,2-dimethylpropylidene)malonate,dimethyl(2-methylbutylidene)malonate,diethyl(2-methylbutylidene)malonate,di-n-propyl(2-methylbutylidene)malonate,diisobutyl(2-methylbutylidene)malonate,di-n-butyl(2-methylbutylidene)malonate,dimethyl(2-ethylbutylidene)malonate, diethyl(2-ethylbutylidene)malonate,di-n-propyl(2-ethylbutylidene)malonate,diisobutyl(2-ethylbutylidene)malonate,di-n-butyl(2-ethylbutylidene)malonate,dimethyl(2-ethylpentylidene)malonate,diethyl(2-ethylpentylidene)malonate,di-n-propyl(2-ethylpentylidene)malonate,diisobutyl(2-ethylpentylidene)malonate,di-n-butyl(2-ethylpentylidene)malonate,dimethyl(2-isopropylbutylidene)malonate,diethyl(2-isopropylbutylidene)malonate,di-n-propyl(2-isopropylbutylidene)malonate,diisobutyl(2-isopropylbutylidene)malonate,di-n-butyl(2-isopropylbutylidene)malonate,dimethyl(3-methylbutylidene)malonate,diethyl(3-methylbutylidene)malonate,di-n-propyl(3-methylbutylidene)malonate,diisobutyl(3-methylbutylidene)malonate,di-n-butyl(3-methylbutylidene)malonate,dimethyl(2,3-dimethylbutylidene)malonate,diethyl(2,3-dimethylbutylidene)malonate,di-n-propyl(2,3-dimethylbutylidene)malonate,diisobutyl(2,3-dimethylbutylidene)malonate,di-n-butyl(2,3-dimethylbutylidene)malonate,dimethyl(2-n-propylbutylidene)malonate,diethyl(2-n-propylbutylidene)malonate,di-n-propyl(2-n-propylbutylidene)malonate,diisobutyl(2-n-propylbutylidene)malonate,di-n-butyl(2-n-propylbutylidene)malonate,dimethyl(2-isobutyl-3-methylbutylidene)malonate,diethyl(2-isobutyl-3-methylbutylidene)malonate,di-n-propyl(2-isobutyl-3-methylbutylidene)malonate,diisobutyl(2-isobutyl-3-methylbutylidene)malonate,di-n-butyl(2-isobutyl-3-methylbutylidene)malonate,dimethyl(2-n-butylpentylidene)malonate,diethyl(2-n-butylpentylidene)malonate,di-n-propyl(2-n-butylpentylidene)malonate,diisobutyl(2-n-butylpentylidene)malonate,di-n-butyl(2-n-butylpentylidene)malonate,dimethyl(2-n-pentylhexylidene)malonate,diethyl(2-n-pentylhexylidene)malonate,di-n-propyl(2-n-pentylhexylidene)malonate,diisobutyl(2-n-pentylhexylidene)malonate,di-n-butyl(2-n-pentylhexylidene)malonate,dimethyl(cyclohexylmethylene)malonate,diethyl(cyclohexylmethylene)malonate,di-n-propyl(cyclohexylmethylene)malonate,diisobutyl(cyclohexylmethylene)malonate,di-n-butyl(cyclohexylmethylene)malonate,dimethyl(cyclopentylmethylene)malonate,diethyl(cyclopentylmethylene)malonate,di-n-propyl(cyclopentylmethylene)malonate,diisobutyl(cyclopentylmethylene)malonate,di-n-butyl(cyclopentylmethylene)malonate,dimethyl(1-methylpropylidene)malonate,diethyl(1-methylpropylidene)malonate,di-n-propyl(1-methylpropylidene)malonate,diisobutyl(1-methylpropylidene)malonate,di-n-butyl(1-methylpropylidene)malonate,diethyl(1-ethylpropylidene)malonate,dimethyl(di-t-butylmethylene)malonate,diethyl(di-t-butylmethylene)malonate, di-n-propyl(di-t-butylmethylene)malonate, diisobutyl(di-t-butylmethylene)malonate,di-n-butyl(di-t-butylmethylene)malonate,dimethyl(diisobutylmethylene)malonate,diethyl(diisobutylmethylene)malonate,di-n-propyl(diisobutylmethylene)malonate,diisobutyl(diisobutylmethylene)malonate,di-n-butyl(diisobutylmethylene)malonate,dimethyl(diisopropylmethylene)malonate,diethyl(diisopropylmethylene)malonate,di-n-propyl(diisopropylmethylene)malonate,diisobutyl(diisopropylmethylene)malonate,di-n-butyl(diisopropylmethylene)malonate,dimethyl(dicyclopentylmethylene)malonate,diethyl(dicyclopentylmethylene)malonate,di-n-propyl(dicyclopentylmethylene)malonate,diisobutyl(dicyclopentylmethylene)malonate,di-n-butyl(dicyclopentylmethylene)malonate,dimethyl(dicyclohexylmethylene)malonate,diethyl(dicyclohexylmethylene)malonate,di-n-propyl(dicyclohexylmethylene)malonate,diisobutyl(dicyclohexylmethylene)malonate,di-n-butyl(dicyclohexylmethylene)malonate, dimethyl benzylidenemalonate,diethyl benzylidenemalonate, di-n-propyl benzylidenemalonate, diisobutylbenzylidenemalonate, di-n-butyl benzylidenemalonate,dimethyl(1-methylbenzylidene)malonate,diethyl(1-methylbenzylidene)malonate,di-n-propyl(1-methylbenzylidene)malonate,diisobutyl(1-methylbenzylidene)malonate,di-n-butyl(1-methylbenzylidene)malonate,dimethyl(1-ethylbenzylidene)malonate,diethyl(1-ethylbenzylidene)malonate,di-n-propyl(1-ethylbenzylidene)malonate,diisobutyl(1-ethylbenzylidene)malonate,di-n-butyl(1-ethylbenzylidene)malonate,dimethyl(1-n-propylbenzylidene)malonate,diethyl(1-n-propylbenzylidene)malonate,di-n-propyl(1-n-propylbenzylidene)malonate,diisobutyl(1-n-propylbenzylidene)malonate,di-n-butyl(1-n-propylbenzylidene)malonate,dimethyl(1-isopropylbenzylidene)malonate,diethyl(1-isopropylbenzylidene)malonate,di-n-propyl(1-isopropylbenzylidene)malonate,diisobutyl(1-isopropylbenzylidene)malonate,di-n-butyl(1-isopropylbenzylidene)malonate,dimethyl(1-n-butylbenzylidene)malonate,diethyl(1-n-butylbenzylidene)malonate,di-n-propyl(1-n-butylbenzylidene)malonate,diisobutyl(1-n-butylbenzylidene)malonate,di-n-butyl(1-n-butylbenzylidene)malonate,dimethyl(1-isobutylbenzylidene)malonate,diethyl(1-isobutylbenzylidene)malonate,di-n-propyl(1-isobutylbenzylidene)malonate,diisobutyl(1-isobutylbenzylidene)malonate,di-n-butyl(1-isobutylbenzylidene)malonate,dimethyl(1-t-butylbenzylidene)malonate,diethyl(1-t-butylbenzylidene)malonate,di-n-propyl(1-t-butylbenzylidene)malonate,diisobutyl(1-t-butylbenzylidene)malonate,di-n-butyl(1-t-butylbenzylidene)malonate,dimethyl(1-n-pentylbenzylidene)malonate,diethyl(1-n-pentylbenzylidene)malonate,di-n-propyl(1-n-pentylbenzylidene)malonate,diisobutyl(1-n-pentylbenzylidene)malonate,di-n-butyl(1-n-pentylbenzylidene)malonate,dimethyl(2-methylphenylmethylene)malonate,diethyl(2-methylphenylmethylene)malonate,di-n-propyl(2-methylphenylmethylene)malonate,diisobutyl(2-methylphenylmethylene)malonate,di-n-butyl(2-methylphenylmethylene)malonate,dimethyl(4-methylphenylmethylene)malonate,dimethyl(2,6-dimethylphenylmethylene)malonate,diethyl(2,6-dimethylphenylmethylene)malonate,di-n-propyl(2,6-dimethylphenylmethylene)malonate,diisobutyl(2,6-dimethylphenylmethylene)malonate,di-n-butyl(2,6-dimethylphenylmethylene)malonate,dimethyl(1-methyl-1-(2-methylphenyl)methylene)malonate,diethyl(1-methyl-1-(2-methylphenyl)methylene)malonate,di-n-propyl(1-methyl-1-(2-methylphenyl)methylene)malonate,diisobutyl(1-methyl-1-(2-methylphenyl)methylene)malonate,di-n-butyl(1-methyl-1-(2-methylphenyl)methylene)malonate,dimethyl(2-methylcyclohexylmethylene)malonate,diethyl(2-methylcyclohexylmethylene)malonate,di-n-propyl(2-methylcyclohexylmethylene)malonate, diisobutyl(2-methylcyclohexylmethylene)malonate,di-n-butyl(2-methylcyclohexylmethylene)malonate,dimethyl(2,6-dimethylcyclohexylmethylene)malonate,diethyl(2,6-dimethylcyclohexylmethylene)malonate,di-n-propyl(2,6-dimethylcyclohexylmethylene)malonate,diisobutyl(2,6-dimethylcyclohexylmethylene)malonate,di-n-butyl(2,6-dimethylcyclohexylmethylene)malonate,dimethyl(1-methyl-1-(2-methylcyclohexyl)methylene)malonate,diethyl(1-methyl-1-(2-methylcyclohexyl)methylene)malonate,di-n-propyl(1-methyl-1-(2-methylcyclohexyl)methylene)malonate,diisobutyl(1-methyl-1-(2-methylcyclohexyl)methylene)malonate,di-n-butyl(1-methyl-1-(2-methylcyclohexyl)methylene)malonate,dimethyl(naphthylmethylene)malonate, diethyl(naphthylmethylene)malonate,di-n-propyl(naphthylmethylene)malonate,diisobutyl(naphthylmethylene)malonate,di-n-butyl(naphthylmethylene)malonate,dimethyl(1-n-hexylbenzylidene)malonate,diethyl(1-n-hexylbenzylidene)malonate,di-n-propyl(1-n-hexylbenzylidene)malonate,diisobutyl(1-n-hexylbenzylidene)malonate, anddi-n-butyl(1-n-hexylbenzylidene)malonate, and the like.

Among these, dialkylmalonic diesters and alkylidenemalonic diesters arepreferable, and dialkylmalonic diesters such as dimethylethylcyclopentylmalonate, diethyl ethylcyclopentylmalonate, dimethyldiisobutylmalonate, and diethyl diisobutylmalonate, andalkylidenemalonic diesters such as dimethyl benzylidenemalonate anddiethyl benzylidenemalonate are more preferable.

Examples of the cycloalkanedicarboxylic diester that may be used as thesecond internal electron donor compound include acyclopentane-1,2-dicarboxylic diester, a cyclopentane-1,3-dicarboxylicdiester, a cyclohexane-1,2-dicarboxylic diester, acyclohexane-1,3-dicarboxylic diester, a cycloheptane-1,2-dicarboxylicdiester, a cycloheptane-1,2-dicarboxylic diester, acyclooctane-1,2-dicarboxylic diester, a cyclooctane-1,3-dicarboxylicdiester, a cyclononane-1,2-dicarboxylic diester, acyclononane-1,3-dicarboxylic diester, a cyclodecane-1,2-dicarboxylicdiester, a cyclodecane-1,3-dicarboxylic diester, and the like.

Among these, compounds having a cycloalkane-1,2-dicarboxylic diesterstructure, such as diethyl cyclopentane-1,2-dicarboxylate, diisopropylcyclopentane-1,2-dicarboxylate, diisobutylcyclopentane-1,2-dicarboxylate, diheptyl cyclopentane-1,2-dicarboxylate,didecyl cyclopentane-1,2-dicarboxylate, di-n-butylcyclopentane-1,2-dicarboxylate, diethyl cyclohexane-1,2-dicarboxylate,di-n-propyl cyclohexane-1,2-dicarboxylate, diisopropylcyclohexane-1,2-dicarboxylate, di-n-butyl cyclohexane-1,2-dicarboxylate,diisobutyl cyclohexane-1,2-dicarboxylate, dihexylcyclohexane-1,2-dicarboxylate, diheptyl cyclohexane-1,2-dicarboxylate,dioctyl cyclohexane-1,2-dicarboxylate, di-2-ethylhexylcyclohexane-1,2-dicarboxylate, didecyl cyclohexane-1,2-dicarboxylate,diethyl cycloheptane-1,2-dicarboxylate, diisopropylcycloheptane-1,2-dicarboxylate, diisobutylcycloheptane-1,2-dicarboxylate, diheptyl cycloheptane-1,2-dicarboxylate,diethyl cyclooctane-1,2-dicarboxylate, and diethylcyclodecane-1,2-dicarboxylate, are preferable.

Examples of the substituted cycloalkanedicarboxylic diester (in whichsome of the hydrogen atoms of the cycloalkyl group are substituted withan alkyl group or the like) that may be used as the second internalelectron donor compound include diethyl3-methylcyclohexane-1,2-dicarboxylate, diethyl4-methylcyclohexane-1,2-dicarboxylate, diethyl5-methylcyclohexane-1,2-dicarboxylate, diethyl3,6-dimethylcyclohexane-1,2-dicarboxylate, di-n-butyl3,6-dimethylcyclohexane-1,2-dicarboxylate, and the like.

Examples of the cycloalkenedicarboxylic diester that may be used as thesecond internal electron donor compound include acyclopentenedicarboxylic diester, a cyclohexenedicarboxylic diester, acycloheptenedicarboxylic diester, a cyclooctenedicarboxylic diester, acyclodecenedicarboxylic diester, a biphenyldicarboxylic diester, and thelike. Specific examples of the cycloalkenedicarboxylic diester include1-cyclohexene-1,2-dicarboxylic diesters such as dimethyl1-cyclohexene-1,2-dicarboxylate, diethyl1-cyclohexene-1,2-dicarboxylate, di-n-propyl1-cyclohexene-1,2-dicarboxylate, diisopropyl1-cyclohexene-1,2-dicarboxylate, di-n-butyl1-cyclohexene-1,2-dicarboxylate, diisobutyl1-cyclohexene-1,2-dicarboxylate, dihexyl1-cyclohexene-1,2-dicarboxylate, diheptyl1-cyclohexene-1,2-dicarboxylate, dioctyl1-cyclohexene-1,2-dicarboxylate, didecyl1-cyclohexene-1,2-dicarboxylate, diethyl1-cyclohexene-1,3-dicarboxylate, and diisobutyl1-cyclohexene-1,3-dicarboxylate, 4-cyclohexene-1,2-dicarboxylic diesterssuch as dimethyl 4-cyclohexene-1,2-dicarboxylate, diethyl4-cyclohexene-1,2-dicarboxylate, di-n-propyl4-cyclohexene-1,2-dicarboxylate, diisopropyl4-cyclohexene-1,2-dicarboxylate, di-n-butyl4-cyclohexene-1,2-dicarboxylate, diisobutyl4-cyclohexene-1,2-dicarboxylate, dihexyl4-cyclohexene-1,2-dicarboxylate, diheptyl4-cyclohexene-1,2-dicarboxylate, dioctyl4-cyclohexene-1,2-dicarboxylate, didecyl4-cyclohexene-1,2-dicarboxylate, diethyl4-cyclohexene-1,3-dicarboxylate, and diisobutyl4-cyclohexene-1,3-dicarboxylate, 3-cyclopentene-1,2-dicarboxylicdiesters such as diethyl 3-cyclopentene-1,2-dicarboxylate, diisopropyl3-cyclopentene-1,2-dicarboxylate, diisobutyl3-cyclopentene-1,2-dicarboxylate, and diheptyl3-cyclopentene-1,2-dicarboxylate, 3-cyclopentene-1,3-dicarboxylicdiesters such as didecyl 3-cyclopentene-1,2-dicarboxylate, diethyl3-cyclopentene-1,3-dicarboxylate, and diisobutyl3-cyclopentene-1,3-dicarboxylate, 4-cycloheptene-1,2-dicarboxylicdiesters such as diethyl 4-cycloheptene-1,2-dicarboxylate, diisopropyl4-cycloheptene-1,2-dicarboxylate, diisobutyl4-cycloheptene-1,2-dicarboxylate, diheptyl4-cycloheptene-1,2-dicarboxylate, and didecyl4-cycloheptene-1,2-dicarboxylate, diethyl4-cycloheptene-1,3-dicarboxylate, diisobutyl4-cycloheptene-1,3-dicarboxylate, diethyl5-cyclooctene-1,2-dicarboxylate, diethyl6-cyclodecene-1,2-dicarboxylate, and the like. It is preferable to useone or more compounds selected from 1-cyclohexene-1,2-dicarboxylicdiesters and 4-cyclohexene-1,2-dicarboxylic diesters.

Examples of the diether that may be used as the second internal electrondonor compound include a compound represented by the following generalformula (VI).

R¹¹ _(k)H_((3-k))C—O—(CR¹²R¹³)_(m)—O—CR¹⁴ _(n)H_((3-n))  (VI)

wherein R¹¹ and R¹⁴ are a halogen atom or an organic group having 1 to20 carbon atoms, provided that R¹¹ and R¹⁴ are either identical ordifferent, and R¹² and R¹³ are a hydrogen atom, an oxygen atom, a sulfuratom, a halogen atom, or an organic group having 1 to 20 carbon atoms,provided that R¹² and R¹³ are either identical or different. The organicgroup having 1 to 20 carbon atoms may include at least one atom selectedfrom an oxygen atom, a fluorine atom, a chlorine atom, a bromine atom,an iodine atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and aboron atom. When a plurality of organic groups having 1 to 20 carbonatoms are present, the plurality of organic groups may bond to eachother to form a ring. k is an integer from 0 to 3. When k is an integerequal to or larger than 2, a plurality of R¹¹ are either identical ordifferent. m is an integer from 1 to 10. When m is an integer equal toor larger than 2, a plurality of R¹² are either identical or different,and a plurality of R¹³ are either identical or different. n is aninteger from 0 to 3. When n is an integer equal to or larger than 2, aplurality of R¹⁴ are either identical or different.

When R¹¹ or R¹⁴ in the general formula (VI) is a halogen atom, thehalogen atom may be a fluorine atom, a chlorine atom, a bromine atom, oran iodine atom. The halogen atom is preferably a fluorine atom, achlorine atom, or a bromine atom.

Examples of the organic group having 1 to 20 carbon atoms represented byR¹¹ or R¹⁴ include a methyl group, an ethyl group, an isopropyl group,an isobutyl group, a n-propyl group, a n-butyl group, a t-butyl group, ahexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group,and a phenyl group. Among these, a methyl group and an ethyl group arepreferable.

When the compound represented by the general formula (VI) includes aplurality of organic groups having 1 to 20 carbon atoms, the pluralityof organic groups may bond to each other to form a ring. In this case,(1) R¹¹ and R¹¹ (when k is equal to or larger than 2), (2) R¹⁴ and R¹⁴(when n is equal to or larger than 2), (3) R¹² and R¹² (when m is equalto or larger than 2), (4) R¹³ and R¹³ (when m is equal to or larger than2), (5) R¹¹ and R¹², (6) R¹¹ and R¹³, (7) R¹¹ and R¹⁴, (8) R¹² and R¹³,(9) R¹² and R¹⁴, or (10) R¹³ and R¹⁴ may bond to each other to form aring. It is preferable that R¹² and R¹³ (see (8)) bond to each other toform a ring. It is more preferable that R¹² and R¹³ bond to each otherto form a fluorene ring or the like.

Specific examples of the compound represented by the general formula(VI) include 2-isopropyl-2-isobutyl-1,3-dimethoxypropane,2,2-diisobutyl-1,3-dimethoxypropane,2-isopropyl-2-isopentyl-1,3-dimethoxypropane,2,2-dicyclohexyl-1,3-dimethoxypropane,2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane,9,9-bis(methoxymethyl)fluorene, 9,9-bis(ethoxymethyl)fluorene,9-methoxy-9-ethoxymethylfluorene,9,9-bis(methoxymethyl)-2,7-dimethylfluorene,9,9-bis(methoxymethyl)-2,6-diisopropylfluorene,9,9-bis(methoxymethyl)-3,6-diisobutylfluorene,9,9-bis(methoxymethyl)-2-isobutyl-7-isopropylfluorene,9,9-bis(methoxymethyl)-2,7-dichlorofluorene,9,9-bis(methoxymethyl)-2-chloro-7-isopropylfluorene, and the like. Amongthese, 2,2-diisobutyl-1,3-dimethoxypropane,2-isopropyl-2-isobutyl-1,3-dimethoxypropane,2-isopropyl-2-isopentyl-1,3-dimethoxypropane,3,3-bis(methoxymethyl)-2,6-dimethylheptane,9,9-bis(methoxymethyl)fluorene, and the like are preferable, and one ormore compounds selected from 2,2-diisobutyl-1,3-dimethoxypropane,2-isopropyl-2-isopentyl-1,3-dimethoxypropane,3,3-bis(methoxymethyl)-2,6-dimethylheptane,9,9-bis(methoxymethyl)fluorene are more preferable. The compoundrepresented by the general formula (VI) is particularly preferably2-isopropyl-2-isobutyl-1,3-dimethoxypropane,2-isopropyl-2-isopentyl-1,3-dimethoxypropane, or9,9-bis(methoxymethyl)fluorene.

k in the general formula (VI) is an integer from 0 to 3, preferably aninteger from 0 to 2, and more preferably 0 or 1. When k is an integerequal to or larger than 2, a plurality of R¹¹ are either identical ordifferent.

m in the general formula (VI) is an integer from 1 to 10, preferably aninteger from 1 to 8, and more preferably an integer from 1 to 6. When mis an integer equal to or larger than 2, a plurality of R¹² are eitheridentical or different, and a plurality of R¹³ are either identical ordifferent.

n in the general formula (VI) is an integer from 0 to 3, preferably aninteger from 0 to 2, and more preferably 0 or 1. When n is an integerequal to or larger than 2, a plurality of R¹⁴ are either identical ordifferent.

Examples of the ether carbonate that may be used as the second internalelectron donor compound include a compound represented by the followinggeneral formula (VII).

R¹⁵—O—C(═O)—O—Z—OR¹⁶  (VII)

wherein R¹⁵ and R¹⁶ are a linear alkyl group having 1 to 20 carbonatoms, a branched alkyl group having 3 to 20 carbon atoms, a vinylgroup, a linear or branched alkenyl group having 3 to 20 carbon atoms, alinear halogen-substituted alkyl group having 1 to 20 carbon atoms, abranched halogen-substituted alkyl group having 3 to 20 carbon atoms, alinear halogen-substituted alkenyl group having 2 to 20 carbon atoms, abranched halogen-substituted alkenyl group having 3 to 20 carbon atoms,a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkenyl grouphaving 3 to 20 carbon atoms, a halogen-substituted cycloalkyl grouphaving 3 to 20 carbon atoms, a halogen-substituted cycloalkenyl grouphaving 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to24 carbon atoms, a halogen-substituted aromatic hydrocarbon group having6 to 24 carbon atoms, a nitrogen atom-containing hydrocarbon grouphaving 2 to 24 carbon atoms that is terminated by a carbon atom(provided that a group that is terminated by a C═N group is excluded),an oxygen atom-containing hydrocarbon group having 2 to 24 carbon atomsthat is terminated by a carbon atom (provided that a group that isterminated by a carbonyl group is excluded), or a phosphorus-containinghydrocarbon group having 2 to 24 carbon atoms that is terminated by acarbon atom (provided that a group that is terminated by a C═P group isexcluded), provided that R¹⁵ and R¹⁶ are either identical or different,and Z is a linking group that bonds the oxygen atoms through a carbonatom or a carbon chain.

Examples of the linear alkyl group having 1 to 20 carbon atoms that maybe represented by R¹⁵ and R¹⁶ in the general formula (VII) include amethyl group, an ethyl group, a n-propyl group, a n-butyl group, an-pentyl group, a n-hexyl group, a n-pentyl group, a n-octyl group, an-nonyl group, a n-decyl group, and the like. Among these, linear alkylgroups having 1 to 12 carbon atoms are preferable.

Examples of the branched alkyl group having 3 to 20 carbon atoms thatmay be represented by R¹⁵ and R¹⁶ include alkyl groups that include asecondary carbon atom or a tertiary carbon atom (e.g., isopropyl group,isobutyl group, t-butyl group, isopentyl group, and neopentyl group).Among these, branched alkyl groups having 3 to 12 carbon atoms arepreferable.

Examples of the linear alkenyl group having 3 to 20 carbon atoms thatmay be represented by R¹⁵ and R¹⁶ include an allyl group, a 3-butenylgroup, a 4-hexenyl group, a 5-hexenyl group, a 7-octenyl group, a10-dodecenyl group, and the like. Among these, linear alkenyl groupshaving 3 to 12 carbon atoms are preferable.

Examples of the branched alkenyl group having 3 to 20 carbon atoms thatmay be represented by R¹⁵ and R¹⁶ include an isopropenyl group, anisobutenyl group, an isopentenyl group, a 2-ethyl-3-hexenyl group, andthe like. Among these, branched alkenyl groups having 3 to 12 carbonatoms are preferable.

Examples of the linear halogen-substituted alkyl group having 1 to 20carbon atoms that may be represented by R¹⁵ and R¹⁶ include a methylhalide group, an ethyl halide group, a n-propyl halide group, a n-butylhalide group, a n-pentyl halide group, a n-hexyl halide group, an-pentyl halide group, a n-octyl halide group, a nonyl halide group, adecyl halide group, a halogen-substituted undecyl group, ahalogen-substituted dodecyl group, and the like. Among these, linearhalogen-substituted alkyl groups having 1 to 12 carbon atoms arepreferable.

Examples of the branched halogen-substituted alkyl group having 3 to 20carbon atoms that may be represented by R¹⁵ and R¹⁶ include an isopropylhalide group, an isobutyl halide group, a 2-ethylhexyl halide group, aneopentyl halide group, and the like. Among these, branchedhalogen-substituted alkyl groups having 3 to 12 carbon atoms arepreferable.

Examples of the linear halogen-substituted alkenyl group having 2 to 20carbon atoms that may be represented by R¹⁵ and R¹⁶ include a2-halogenated vinyl group, a 3-halogenated allyl group, a 3-halogenated2-butenyl group, a 4-halogenated 3-butenyl group, a perhalogenated2-butenyl group, a 6-halogenated 4-hexenyl group, a 3-trihalogenatedmethyl-2-propenyl group, and the like. Among these, linearhalogen-substituted alkenyl groups having 2 to 12 carbon atoms arepreferable.

Examples of the branched halogen-substituted alkenyl group having 3 to20 carbon atoms that may be represented by R¹⁵ and R¹⁶ include a3-trihalogenated 2-butenyl group, a 2-pentahalogenated ethyl-3-hexenylgroup, a 6-halogenated 3-ethyl-4-hexenyl group, a 3-halogenatedisobutenyl group, and the like. Among these, branchedhalogen-substituted alkenyl groups having 3 to 12 carbon atoms arepreferable.

Examples of the cycloalkyl group having 3 to 20 carbon atoms that may berepresented by R¹⁵ and R¹⁶ include a cyclopropyl group, a cyclobutylgroup, a cyclopentyl group, a tetramethylcyclopentyl group, a cyclohexylgroup, a methylcyclohexyl group, a cycloheptyl group, a cyclooctylgroup, a cyclononyl group, a cyclodecyl group, a butylcyclopentyl group,and the like. Among these, cycloalkyl groups having 3 to 12 carbon atomsare preferable.

Examples of the cycloalkenyl group having 3 to 20 carbon atoms that maybe represented by R¹⁵ and R¹⁶ include a cyclopropenyl group, acyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, anorbornene group, and the like. Among these, cycloalkenyl groups having3 to 12 carbon atoms are preferable.

Examples of the halogen-substituted cycloalkyl group having 3 to 20carbon atoms that may be represented by R¹⁵ and R¹⁶ include ahalogen-substituted cyclopropyl group, a halogen-substituted cyclobutylgroup, a halogen-substituted cyclopentyl group, a halogen-substitutedtrimethylcyclopentyl group, a halogen-substituted cyclohexyl group, ahalogen-substituted methylcyclohexyl group, a halogen-substitutedcycloheptyl group, a halogen-substituted cyclooctyl group, ahalogen-substituted cyclononyl group, a halogen-substituted cyclodecylgroup, a halogen-substituted butylcyclopentyl group, and the like. Amongthese, halogen-substituted cycloalkyl groups having 3 to 12 carbon atomsare preferable.

Examples of the halogen-substituted cycloalkenyl group having 3 to 20carbon atoms that may be represented by R¹⁵ and R¹⁶ include ahalogen-substituted cyclopropenyl group, a halogen-substitutedcyclobutenyl group, a halogen-substituted cyclopentenyl group, ahalogen-substituted trimethylcyclopentenyl group, a halogen-substitutedcyclohexenyl group, a halogen-substituted methylcyclohexenyl group, ahalogen-substituted cycloheptenyl group, a halogen-substitutedcyclooctenyl group, and halogen-substituted cyclononenyl group, ahalogen-substituted cyclodecenyl group, a halogen-substitutedbutylcyclopentenyl group, and the like. Among these, halogen-substitutedcycloalkenyl groups having 3 to 12 carbon atoms are preferable.

Examples of the aromatic hydrocarbon group having 6 to 24 carbon atomsthat may be represented by R¹⁵ and R¹⁶ include a phenyl group, amethylphenyl group, a dimethylphenyl group, an ethylphenyl group, abenzyl group, a 1-phenylethyl group, a 2-phenylethyl group, a2-phenylpropyl group, a 1-phenylbutyl group, a 4-phenylbutyl group, a2-phenylheptyl group, a tolyl group, a xylyl group, a naphthyl group, a1,8-dimethylnaphthyl group, and the like. Among these, aromatichydrocarbon groups having 6 to 12 carbon atoms are preferable.

Examples of the halogen-substituted aromatic hydrocarbon group having 6to 24 carbon atoms that may be represented by R¹⁵ and R¹⁶ include aphenyl halide group, a methylphenyl halide group, a methylphenyltrihalide group, a benzyl perhalide group, a phenyl perhalide group, a2-phenyl-2-halogenated ethyl group, a naphthyl perhalide group, a4-phenyl-2,3-dihalogenated butyl group, and the like. Among these,halogen-substituted aromatic hydrocarbon groups having 6 to 12 carbonatoms are preferable.

When R¹⁵ or R¹⁶ in the general formula (VII) is a group that includes ahalogen atom, the halogen atom may be a fluorine atom, a chlorine atom,a bromine atom, or an iodine atom. The halogen atom is preferably afluorine atom, a chlorine atom, or a bromine atom.

Examples of the phosphorus-containing hydrocarbon group having 2 to 24carbon atoms terminated by a carbon atom (provided that a group that isterminated by a C═P group is excluded) that may be represented by R¹⁵and R¹⁶ include dialkylphosphinoalkyl groups such as adimethylphosphinomethyl group, a dibutylphosphinomethyl group, adicyclohexylphosphinomethyl group, a dimethylphosphinoethyl group, adibutylphosphinoethyl group, and a dicyclohexylphosphinoethyl group,diarylphosphinoalkyl groups such as a diphenylphosphinomethyl group anda ditolylphosphinomethyl group, phosphino group-substituted aryl groupssuch as a dimethylphosphinophenyl group and a diethylphosphinophenylgroup, and the like. Among these, phosphorus-containing hydrocarbongroups having 2 to 12 carbon atoms are preferable.

Note that the expression “terminated by” used herein in connection withR¹⁵ and R¹⁶ means that R¹⁵ or R¹⁶ is bonded to the adjacent oxygen atomthrough an atom or a group by which R¹⁵ or R¹⁶ is terminated.

R¹⁵ is preferably a linear alkyl group having 1 to 12 carbon atoms, abranched alkyl group having 3 to 12 carbon atoms, a vinyl group, alinear or branched alkenyl group having 3 to 12 carbon atoms, a linearhalogen-substituted alkyl group having 1 to 12 carbon atoms, a branchedhalogen-substituted alkyl group having 3 to 12 carbon atoms, a linear orbranched halogen-substituted alkenyl group having 3 to 12 carbon atoms,a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl grouphaving 3 to 12 carbon atoms, a halogen-substituted cycloalkyl grouphaving 3 to 12 carbon atoms, a halogen-substituted cycloalkenyl grouphaving 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6to 12 carbon atoms, more preferably a linear alkyl group having 1 to 12carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, avinyl group, a linear or branched alkenyl group having 3 to 12 carbonatoms, a linear halogen-substituted alkyl group having 1 to 12 carbonatoms, a branched halogen-substituted alkyl group having 3 to 12 carbonatoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenylgroup having 3 to 12 carbon atoms, or an aromatic hydrocarbon grouphaving 6 to 12 carbon atoms, and still more preferably a linear alkylgroup having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbonatoms.

R¹⁶ is preferably a linear alkyl group having 1 to 12 carbon atoms, abranched alkyl group having 3 to 12 carbon atoms that is terminated by—CH₂—, a vinyl group, a linear alkenyl group having 3 to 12 carbonatoms, a branched alkenyl group having 3 to 12 carbon atoms that isterminated by —CH₂—, a linear halogen-substituted alkyl group having 1to 12 carbon atoms, a branched halogen-substituted alkyl group having 3to 12 carbon atoms that is terminated by —CH₂—, a linearhalogen-substituted alkenyl group having 3 to 12 carbon atoms, abranched halogen-substituted alkenyl group having 3 to 12 carbon atomsthat is terminated by —CH₂—, a cycloalkyl group having 4 to 12 carbonatoms that is terminated by —CH₂—, a cycloalkenyl group having 4 to 12carbon atoms that is terminated by —CH₂—, a halogen-substitutedcycloalkyl group having 4 to 12 carbon atoms that is terminated by—CH₂—, a halogen-substituted cycloalkenyl group having 4 to 12 carbonatoms that is terminated by —CH₂—, or an aromatic hydrocarbon grouphaving 7 to 12 carbon atoms that is terminated by —CH₂—, more preferablya linear alkyl group having 1 to 12 carbon atoms, a branched alkyl grouphaving 3 to 12 carbon atoms that is terminated by —CH₂—, a branchedalkenyl group having 3 to 12 carbon atoms that is terminated by —CH₂—, alinear halogen-substituted alkyl group having 1 to 12 carbon atoms thatis terminated by —CH₂—, a branched halogen-substituted alkyl grouphaving 3 to 12 carbon atoms that is terminated by —CH₂—, a branchedhalogen-substituted alkenyl group having 3 to 12 carbon atoms that isterminated by —CH₂—, a cycloalkyl group having 4 to 12 carbon atoms thatis terminated by —CH₂—, a cycloalkenyl group having 4 to 12 carbon atomsthat is terminated by —CH₂—, a halogen-substituted cycloalkyl grouphaving 4 to 12 carbon atoms that is terminated by —CH₂—, ahalogen-substituted cycloalkenyl group having 4 to 12 carbon atoms thatis terminated by —CH₂—, or an aromatic hydrocarbon group having 7 to 12carbon atoms that is terminated by —CH₂—, and still more preferably alinear hydrocarbon group having 1 to 12 carbon atoms, a branched alkylgroup having 3 to 12 carbon atoms that is terminated by —CH₂—, or anaromatic hydrocarbon group having 7 to 12 carbon atoms that isterminated by —CH₂—.

Note that the expression “terminated by” used herein in connection withR¹⁶ means that R¹⁶ is bonded to the adjacent oxygen atom included in thecompound represented by the general formula (VII) through an atom or agroup by which R¹⁶ is terminated.

Examples of a combination of R¹⁵ and R¹⁶ include combinations of groupsmentioned above as preferable groups. It is preferable that R¹⁵ and R¹⁶be a combination of groups mentioned above as more preferable groups.

Z in the general formula (VII) is a divalent linking group that bondsthe carbonate group and the ether group (OR¹⁶) through a carbon atom ora carbon chain. Z may be a linking group that bonds the two oxygen atomsbonded to Z (i.e., bonded through Z) through a carbon chain, forexample. It is preferable that Z be a linking group in which the carbonchain includes two carbon atoms.

Z is preferably a linear alkylene group having 1 to 20 carbon atoms, abranched alkylene group having 3 to 20 carbon atoms, a vinylene group, alinear or branched alkenylene group having 3 to 20 carbon atoms, alinear halogen-substituted alkylene group having 1 to 20 carbon atoms, abranched halogen-substituted alkylene group having 3 to 20 carbon atoms,a linear or branched halogen-substituted alkenylene group having 3 to 20carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, acycloalkenylene group having 3 to 20 carbon atoms, a halogen-substitutedcycloalkylene group having 3 to 20 carbon atoms, a halogen-substitutedcycloalkenylene group having 3 to 20 carbon atoms, an aromatichydrocarbon group having 6 to 24 carbon atoms, a halogen-substitutedaromatic hydrocarbon group having 6 to 24 carbon atoms, a nitrogenatom-containing hydrocarbon group having 1 to 24 carbon atoms, an oxygenatom-containing hydrocarbon group having 1 to 24 carbon atoms, or aphosphorus-containing hydrocarbon group having 1 to 24 carbon atoms.

Z is more preferably an ethylene group having 2 carbon atoms, a branchedalkylene group having 3 to 12 carbon atoms, a vinylene group, a linearor branched alkenylene group having 3 to 12 carbon atoms, a linearhalogen-substituted alkylene group having 2 to 12 carbon atoms, abranched halogen-substituted alkylene group having 3 to 12 carbon atoms,a linear or branched halogen-substituted alkenylene group having 3 to 12carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, acycloalkenylene group having 3 to 12 carbon atoms, a halogen-substitutedcycloalkylene group having 3 to 12 carbon atoms, a halogen-substitutedcycloalkenylene group having 3 to 12 carbon atoms, an aromatichydrocarbon group having 6 to 12 carbon atoms, a halogen-substitutedaromatic hydrocarbon group having 6 to 12 carbon atoms, a nitrogenatom-containing hydrocarbon group having 2 to 12 carbon atoms, an oxygenatom-containing hydrocarbon group having 2 to 12 carbon atoms, or aphosphorus-containing hydrocarbon group having 2 to 12 carbon atoms, andstill more preferably a bidentate linking group selected from anethylene group having 2 carbon atoms and a branched alkylene grouphaving 3 to 12 carbon atoms. Note that the term “bidentate linkinggroup” used herein refers to a group in which two oxygen atoms bonded toZ are bonded through a carbon chain, and the carbon chain includes twocarbon atoms.

Examples of the linear alkylene group having 1 to 20 carbon atomsrepresented by Z include an ethylene group, a trimethylene group, atetramethylene group, a pentamethylene group, a hexamethylene group, aheptamethylene group, an octamethylene group, a nonamethylene group, adecamethylene group, an undecamethylene group, a dodecamethylene group,a tridecamethylene group, a tetradecamethylene group, and the like.Among these, linear alkylene groups having 2 to 12 carbon atoms arepreferable, and an ethylene group is more preferable.

Examples of the branched alkylene group having 3 to 20 carbon atomsrepresented by Z include a 1-methylethylene group, a2-methyltrimethylene group, a 2-methyltetramethylene group, a2-methylpentamethylene group, a 3-methylhexamethylene group, a4-methylheptamethylene group, a 4-methyloctamethylene group, a5-methylnonamethylene group, a 5-methyldecamethylene group, a6-methylundecamethylene group, a 7-methyldodecamethylene group, a7-methyltridecamethylene group, and the like. Among these, branchedalkylene groups having 3 to 12 carbon atoms are preferable, and a1-methylethylene group, a 2-methylethylene group, and a 1-ethylethylenegroup are more preferable.

Examples of the linear alkenylene group having 3 to 20 carbon atomsrepresented by Z include a propenylene group, a butenylene group, ahexenylene group, an octenylene group, an octadecenylene group, and thelike. Among these, linear alkenylene groups having 3 to 12 carbon atomsare preferable.

Examples of the branched alkenylene group having 3 to 20 carbon atomsrepresented by Z include an isopropenylene group, a 1-ethylethenylenegroup, a 2-methylpropenylene group, a 2,2-dimethylbutenylene group, a3-methyl-2-butenylene group, a 3-ethyl-2-butenylene group, a2-methyloctenylene group, a 2,4-dimethyl-2-butenylene group, and thelike. Among these, branched alkenylene groups having 3 to 12 carbonatoms that includes an ethenylene linking group are preferable, and anisopropenylene group and a 1-ethylethenylene group are more preferable.

Examples of the linear halogen-substituted alkylene group having 1 to 20carbon atoms represented by Z include a dichloromethylene group, achloromethylene group, a dichloromethylene group, a tetrachloroethylenegroup, and the like. Among these, linear halogen-substituted alkylenegroups having 3 to 12 carbon atoms are preferable, and a chloroethylenegroup, a fluoroethylene group, a dichloroethylene group, adifluoroethylene group, and a tetrafluoroethylene group are morepreferable.

Examples of the branched halogen-substituted alkylene group having 1 to20 carbon atoms represented by Z include a 1,2-bischloromethylethylenegroup, a 2,2-bis(chloromethyl)propylene group, a1,2-bisdichloromethylethylene group, a 1,2-bis(trichloromethyl)ethylenegroup, a 2,2-dichloropropylene group, a 1,1,2,2-tetrachloroethylenegroup, a 1-trifluoromethylethylene group, a 1-pentafluorophenylethylenegroup, and the like. Among these, branched halogen-substituted alkylenegroups having 3 to 12 carbon atoms are preferable, and a1-chloroethylethylene group, a 1-trifluoromethylethylene group, and a1,2-bis(chloromethyl)ethylene group are more preferable.

Examples of the linear halogen-substituted alkenylene group having 1 to20 carbon atoms represented by Z include a dichloroethenylene group, adifluoroethenylene group, a 3,3-dichloropropenylene group, a1,2-difluoropropenylene group, and the like. Among these, linearhalogen-substituted alkenylene groups having 3 to 12 carbon atoms arepreferable, and a dichloroethenylene group and a difluoroethenylenegroup are more preferable.

Examples of the branched halogen-substituted alkylene group having 1 to20 carbon atoms represented by Z include a 3,4-dichloro-1,2-butylenegroup, a 2,2-dichloro-1,3-butylene group, a 1,2-difluoro-1,2-propylenegroup, and the like. Among these, branched halogen-substituted alkylenegroups having 3 to 12 carbon atoms are preferable, and achloromethylethenylene group, a trifluoromethylethenylene group, a3,4-dichloro-1,2-butenylene group are more preferable.

Examples of the cycloalkylene group having 3 to 20 carbon atomsrepresented by Z include a cyclopentylene group, a cyclohexylene group,a cyclopropylene group, a 2-methylcyclopropylene group, a cyclobutylenegroup, a 2,2-dimethylcyclobutylene group, a 2,3-dimethylcyclopentylenegroup, a 1,3,3-trimethylcyclohexylene group, a cyclooctylene group, andthe like. Among these, cycloalkylene groups having 3 to 12 carbon atomsare preferable, and a 1,2-cycloalkylene group and a hydrocarbongroup-substituted 1,2-cycloalkylene group are more preferable.

Examples of the cycloalkenylene group having 3 to 20 carbon atomsrepresented by Z include a cyclopentenylene group, a2,4-cyclopentadienylene group, a cyclohexenylene group, a1,4-cyclohexadienyl group, a cycloheptenylene group, amethylcyclopentenylene group, a methylcyclohexenylene group, amethylcycloheptenylene group, a dicyclodecylene group, atricyclodecylene group, and the like. Among these, cycloalkenylenegroups having 3 to 12 carbon atoms are preferable, and a1,2-cycloalkenylene group and a hydrocarbon group-substituted1,2-cycloalkenylene group are more preferable.

Examples of the halogen-substituted cycloalkylene group having 3 to 20carbon atoms represented by Z include a 3-chloro-1,2-cyclopentylenegroup, a 3,4,5,6-tetrachloro-1,2-cyclohexylene group, a3,3-dichloro-1,2-cyclopropylene group, a 2-chloromethylcyclopropylenegroup, a 3,4-dichloro-1,2-cyclobutylene group, a3,3-bis(dichloromethyl)-1,2-cyclobutylene group, a2,3-bis(dichloromethyl)cyclopentylene group, a1,3,3-tris(fluoromethyl)-1,2-cyclohexylene group, a3-trichloromethyl-1,2-cyclooctylene group, and the like. Among these,halogen-substituted cycloalkylene groups having 3 to 12 carbon atoms arepreferable.

Examples of the halogen-substituted cycloalkenylene group having 3 to 20carbon atoms represented by Z include a 5-chloro-1,2-cyclo-4-hexenylenegroup, a 3,3,4,4-tetrafluoro-1,2-cyclo-6-octenylene group, and the like.Among these, halogen-substituted cycloalkenylene groups having 3 to 12carbon atoms are preferable.

Examples of the aromatic hydrocarbon group having 6 to 24 carbon atomsrepresented by Z include a 1,2-phenylene group, a 3-methyl-1,2-phenylenegroup, a 3,6-dimethyl-1,2-phenylene group, a 1,2-naphthylene group, a2,3-naphthylene group, a 5-methyl-1,2-naphthylene group, a9,10-phenanthrylene group, a 1,2-anthracenylene group, and the like.Among these, aromatic hydrocarbon groups having 6 to 12 carbon atoms arepreferable.

Examples of the halogen-substituted aromatic hydrocarbon group having 6to 24 carbon atoms represented by Z include a 3-chloro-1,2-phenylenegroup, a 3-chloromethyl-1,2-phenylene group, a3,6-dichloro-1,2-phenylene group, a3,6-dichloro-4,5-dimethyl-1,2-phenylene group, a3-chloro-1,2-naphthylene group, a 3-fluoro-1,2-naphthylene group, a3,6-dichloro-1,2-phenylene group, a 3,6-difluoro-1,2-phenylene group, a3,6-dibromo-1,2-phenylene group, a 1-chloro-2,3-naphthylene group, a5-chloro-1,2-naphthylene group, a 2,6-dichloro-9,10-phenanthrylenegroup, a 5,6-dichloro-1,2-anthracenylene group, a5,6-difluoro-1,2-anthracenylene, and the like. Among these,halogen-substituted aromatic hydrocarbon groups having 6 to 12 carbonatoms are preferable.

Examples of the nitrogen atom-containing hydrocarbon group having 1 to24 carbon atoms represented by Z include a 1-dimethylaminoethylenegroup, a 1,2-bisdimethylaminoethylene group, a 1-diethylaminoethylenegroup, a 2-diethylamino-1,3-propylene group, a2-ethylamino-1,3-propylene group, a 4-dimethylamino-1,2-phenylene group,a 4,5-bis(dimethylamino)phenylene group, and the like. Among these,nitrogen atom-containing hydrocarbon groups having 2 to 12 carbon atomsare preferable.

Examples of the oxygen atom-containing hydrocarbon group having 1 to 24carbon atoms that may be represented by Z include a 1-methoxyethylenegroup, a 2,2-dimethoxy-1,3-propanylene group, a 2-ethoxy-1,3-propanylenegroup, a 2-t-butoxy-1,3-propanylene group, a 2,3-dimethoxy-2,3-butylenegroup, a 4-methoxy-1,2-phenylene group, and the like. Among these,oxygen atom-containing hydrocarbon groups having 2 to 12 carbon atomsare preferable.

Examples of the phosphorus-containing hydrocarbon group having 1 to 24carbon atoms that may be represented by Z include a1-dimethylphosphinoethylene group, a2,2-bis(dimethylphosphino)-1,3-propanylene group, a2-diethylphosphino-1,3-propanylene group, a2-t-butoxymethylphosphino-1,3-propanylene group, a2,3-bis(diphenylphospino)-2,3-butylene group, a4-methylphosphate-1,2-phenylene group, and the like. Among these,phosphorus-containing hydrocarbon groups having 1 to 12 carbon atoms arepreferable.

When Z is a cyclic group (e.g., cycloalkylene group, cycloalkenylenegroup, halogen-substituted cycloalkylene group, halogen-substitutedcycloalkenylene group, aromatic hydrocarbon group, orhalogen-substituted aromatic hydrocarbon group), the two oxygen atomsbonded to Z may be bonded through two adjacent carbon atoms that formthe cyclic group.

Specific examples of the compound represented by the general formula(VII) include 2-methoxyethyl methyl carbonate, 2-ethoxyethyl methylcarbonate, 2-propoxyethyl methyl carbonate, 2-(2-ethoxyethyloxyl)ethylmethyl carbonate, 2-benzyloxyethyl methyl carbonate, (2-methoxypropyl)methyl carbonate, 2-ethoxypropyl methyl carbonate,2-methyl(2-methoxy)butyl methyl carbonate, 2-methyl(2-ethoxy)butylmethyl carbonate, 2-methyl(2-methoxy)pentyl methyl carbonate,2-methyl(2-ethoxy)pentyl methyl carbonate, 1-phenyl(2-methoxy) propylcarbonate, 1-phenyl(2-ethoxy)propyl methyl carbonate,1-phenyl(2-benzyloxy)propyl methyl carbonate, 1-phenyl(2-methoxy)ethylmethyl carbonate, 1-phenyl(2-ethoxy)ethyl methyl carbonate,1-methyl-1-phenyl(2-methoxy)ethyl methyl carbonate,1-methyl-1-phenyl(2-ethoxy)ethyl methyl carbonate,1-methyl-1-phenyl(2-benzyloxy)ethyl methyl carbonate,1-methyl-1-phenyl(2-(2-ethoxyethyloxy))ethyl methyl carbonate,2-methoxyethyl ethyl carbonate, 2-ethoxyethyl ethyl carbonate,1-phenyl(2-methoxy)ethyl ethyl carbonate, 1-phenyl(2-ethoxy)ethyl ethylcarbonate, 1-phenyl(2-propoxy)ethyl ethyl carbonate,1-phenyl(2-butoxy)ethyl ethyl carbonate, 1-phenyl(2-isobutyloxy)ethylethyl carbonate, 1-phenyl(2-(2-ethoxyethyloxy))ethyl ethyl carbonate,1-methyl-1-phenyl(2-methoxy)ethyl ethyl carbonate,1-methyl-1-phenyl(2-ethoxy)ethyl ethyl carbonate,1-methyl-1-phenyl(2-propoxy)ethyl ethyl carbonate,1-methyl-1-phenyl(2-butoxy)ethyl ethyl carbonate,1-methyl-1-phenyl(2-isobutyloxy)ethyl ethyl carbonate,1-methyl-1-phenyl(2-benzyloxy)ethyl ethyl carbonate,1-methyl-1-phenyl(2-(2-ethoxyethyloxy))ethyl ethyl carbonate,2-methoxyethyl phenyl carbonate, 2-ethoxyethyl phenyl carbonate,2-propoxyethyl phenyl carbonate, 2-butoxyethyl phenyl carbonate,2-isobutyloxyethyl phenyl carbonate, 2-benzyloxyethyl phenyl carbonate,2-(2-ethoxyethyloxyl)ethyl phenyl carbonate, 2-methoxyethylp-methylphenyl carbonate, 2-ethoxyethyl p-methylphenyl carbonate,2-propoxyethyl p-methylphenyl carbonate, 2-butoxyethyl p-methylphenylcarbonate, 2-isobutyloxyethyl p-methylphenyl carbonate, 2-benzyloxyethylp-methylphenyl carbonate, 2-(2-ethoxyethyloxyl)ethyl p-methylphenylcarbonate, 2-methoxyethyl o-methylphenyl carbonate, 2-ethoxyethylo-methylphenyl carbonate, 2-propoxyethyl o-methylphenyl carbonate,2-butoxyethyl o-methylphenyl carbonate, 2-isobutyloxyethylo-methylphenyl carbonate, 2-benzyloxyethyl o-methylphenyl carbonate,2-(2-ethoxyethyloxyl)ethyl o-methylphenyl carbonate, 2-methoxyethylo,p-dimethylphenyl carbonate, 2-ethoxyethyl o,p-dimethylphenylcarbonate, 2-propoxyethyl o,p-dimethylphenyl carbonate, 2-butoxyethylo,p-dimethylphenyl carbonate, 2-isobutyloxyethyl o,p-dimethylphenylcarbonate, 2-benzyloxyethyl o,p-dimethylphenyl carbonate,2-(2-ethoxyethyloxyl)ethyl o,p-dimethylphenyl carbonate, 2-methoxypropylphenyl carbonate, 2-ethoxypropyl phenyl carbonate, 2-propoxypropylphenyl carbonate, 2-butoxypropyl phenyl carbonate, 2-isobutyloxypropylphenyl carbonate, 2-(2-ethoxyethyloxyl)propyl phenyl carbonate,2-phenyl(2-methoxy)ethyl phenyl carbonate, 2-phenyl(2-ethoxy)ethylphenyl carbonate, 2-phenyl(2-propoxy)ethyl phenyl carbonate,2-phenyl(2-butoxy)ethyl phenyl carbonate, 2-phenyl(2-isobutyloxy)ethylphenyl carbonate, 2-phenyl(2-(2-ethoxyethyloxy))ethyl phenyl carbonate,1-phenyl(2-methoxy)propyl phenyl carbonate, 1-phenyl(2-ethoxy)propylphenyl carbonate, 1-phenyl(2-propoxy)propyl phenyl carbonate,1-phenyl(2-isobutyloxy)propyl phenyl carbonate, 1-phenyl(2-methoxy)ethylphenyl carbonate, 1-phenyl(2-ethoxy)ethyl phenyl carbonate,1-phenyl(2-propoxy)ethyl phenyl carbonate, 1-phenyl(2-butoxy)ethylphenyl carbonate, 1-phenyl(2-isobutyloxy)ethyl phenyl carbonate,1-phenyl(2-(2-ethoxyethyloxy))ethyl phenyl carbonate,1-methyl-1-phenyl(2-methoxy)ethylphenyl carbonate,1-methyl-1-phenyl(2-ethoxy) ethyl phenyl carbonate,1-methyl-1-phenyl(2-propoxy)ethyl phenyl carbonate,1-methyl-1-phenyl(2-butoxy)ethyl phenyl carbonate,1-methyl-1-phenyl(2-isobutyloxy)ethyl phenyl carbonate,1-methyl-1-phenyl(2-benzyloxy)ethyl phenyl carbonate, and1-methyl-1-phenyl(2-(2-ethoxyethyloxy))ethyl phenyl carbonate. Amongthese, one or more compounds selected from (2-ethoxyethyl) methylcarbonate, (2-ethoxyethyl) ethyl carbonate, (2-propoxyethyl) propylcarbonate, (2-butoxyethyl) butyl carbonate, (2-butoxyethyl) ethylcarbonate, (2-ethoxyethyl) propyl carbonate, (2-ethoxyethyl) phenylcarbonate, and (2-ethoxyethyl) p-methylphenyl carbonate are preferable.

Among these, (2-ethoxyethyl) methyl carbonate, (2-ethoxyethyl) ethylcarbonate, and (2-ethoxyethyl) phenyl carbonate are particularlypreferable.

The second internal electron donor compound is particularly preferablyone or more compounds selected from diethyl phthalate, di-n-propylphthalate, di-n-butyl phthalate, diisobutyl phthalate, dimethyldiisobutylmalonate, diethyl diisobutylmalonate, dimethylbenzylidenemalonate, diethyl benzylidenemalonate, (2-ethoxyethyl) methylcarbonate, (2-ethoxyethyl) ethyl carbonate, and (2-ethoxyethyl) phenylcarbonate.

In the second step included in the method for producing a solid catalystcomponent for olefin polymerization according to one embodiment of theinvention, the tetravalent titanium halide compound and one or moresecond internal electron donor compounds are brought into contact withthe reaction product obtained by the first step to effect a reaction.

In the second step, the tetravalent titanium halide compound and thesecond internal electron donor compound may preferably be brought intocontact with the reaction product obtained by the first step byappropriately mixing the tetravalent titanium halide compound, thesecond internal electron donor compound, and the reaction productobtained by the first step in the presence of the inert organic solventsimilar to those mentioned above in connection with the first step.

In the second step, the components may be brought into contact with thereaction product obtained by the first step under arbitrary conditions.Contact/reaction conditions similar to those employed in the first stepmay be used.

When bringing the tetravalent titanium halide compound and the secondinternal electron donor compound into contact with the reaction productobtained by the first step to effect a reaction, the tetravalenttitanium halide compound is preferably used in an amount of 0.1 to 50mol, more preferably 0.2 to 20 mol, and still more preferably 0.3 to 10mol, based on 1 mol of the magnesium compound (that is added in thefirst step).

When bringing the tetravalent titanium halide compound and the secondinternal electron donor compound into contact with the reaction productobtained by the first step to effect a reaction, the molar ratio (molarquantity of the second internal electron donor compound/molar quantityof the magnesium compound) of the second internal electron donorcompound to the magnesium compound (that is added in the first step) ispreferably 0.001 to 10, more preferably 0.001 to 1, more preferably0.002 to 1, still more preferably 0.002 to 0.6, and yet more preferably0.003 to 0.6.

When bringing the tetravalent titanium halide compound and the secondinternal electron donor compound into contact with the reaction productobtained by the first step to effect a reaction, the molar ratio (molarquantity of the second internal electron donor compound/molar quantityof the aromatic dicarboxylic diester represented by the general formula(I) (first internal electron donor compound)) of the second internalelectron donor compound to the aromatic dicarboxylic diester representedby the general formula (I) (first internal electron donor compound)(that is added in the first step) is preferably 0.01 to 0.9, morepreferably 0.01 to 0.6, and still more preferably 0.02 to 0.4.

When the molar ratio (molar quantity of the second internal electrondonor compound/molar quantity of the aromatic dicarboxylic diesterrepresented by the general formula (I) (first internal electron donorcompound)) of the second internal electron donor compound to thearomatic dicarboxylic diester represented by the general formula (I)(first internal electron donor compound) is within the above range, itis possible to easily suppress a situation in which a large amount of acomplex compound of the second internal electron donor compound and thetetravalent titanium halide compound is formed, and easily improvepolymerization activity and stereoregularity when polymerizing an olefinusing the resulting solid catalyst component.

When using the inert organic solvent in the second step, the inertorganic solvent is preferably used in an amount of 0.001 to 500 mol,more preferably 0.5 to 100 mol, and still more preferably 1.0 to 20 mol,based on 1 mol of the magnesium compound (that is added in the firststep).

When implementing the method for producing a solid catalyst componentfor olefin polymerization according to one embodiment of the invention,it is preferable to add the necessary amount of the magnesium compoundto the reaction system in the first step, and not add the magnesiumcompound to the reaction system in the second step taking account of thereaction efficiency and the like.

In the second step, it is preferable to bring the components intocontact with each other with stirring in a vessel equipped with astirrer that contains an inert gas atmosphere from which water and thelike have been removed.

After completion of the reaction, it is preferable to wash the reactionproduct after allowing the reaction mixture to stand, appropriatelyremoving the supernatant liquid to achieve a wet state (slurry state),and optionally drying the reaction mixture by hot-air drying or thelike.

In the second step, the resulting reaction product is washed aftercompletion of the reaction.

The reaction product is normally washed using a washing agent. Examplesof the washing agent include those mentioned above in connection withthe first step.

The washing temperature, the washing method, the amount of washingagent, the number of washing operations, and the like employed in thesecond step are the same as those described above in connection with thefirst step.

According to the method for producing a solid catalyst component forolefin polymerization according to one embodiment of the invention, itis possible to remove unreacted raw material components, reactionby-products (e.g., alkoxytitanium halide and titaniumtetrachloride-carboxylic acid complex), and impurities that remain inthe reaction product by washing the reaction product in the second stepafter bringing the components into contact with each other to effect areaction.

In the second step included in the method for producing a solid catalystcomponent for olefin polymerization according to one embodiment of theinvention, the washed product may be brought into contact with atetravalent titanium halide compound, and washed (post-treatment), forexample. The product may be washed in the same manner as describedabove.

When implementing the method for producing a solid catalyst componentfor olefin polymerization according to one embodiment of the invention,the product subjected to the post-treatment in the second step may besubjected to the third step (described below). Note that it ispreferable to subject the product directly to the third step withoutsubjecting the product to the post-treatment and the like.

After completion of the reaction, the suspension obtained by washing maybe allowed to stand, and the supernatant liquid may be removed toachieve a wet state (slurry state). The reaction mixture may optionallybe dried by hot-air drying or the like. The suspension obtained bywashing may be subjected directly to the third step. When subjecting thesuspension obtained by washing directly to the third step, the dryingtreatment can be omitted, and it is unnecessary to add an inert organicsolvent in the third step.

Third Step

In the third step included in the method for producing a solid catalystcomponent for olefin polymerization according to one embodiment of theinvention, one or more third internal electron donor compounds arebrought into contact with the product obtained by the second step toeffect a reaction.

Examples of the third internal electron donor compound used inconnection with the method for producing a solid catalyst component forolefin polymerization according to one embodiment of the inventioninclude those mentioned above in connection with the second internalelectron donor compound.

The third electron donor compound may be the same as or different fromthe first electron donor compound, and may be the same as or differentfrom the second electron donor compound.

In the third step included in the method for producing a solid catalystcomponent for olefin polymerization according to one embodiment of theinvention, the third internal electron donor compound is brought intocontact with the reaction product obtained by the second step to effecta reaction.

In the third step, the third internal electron donor compound maypreferably be brought into contact with the reaction product obtained bythe second step by appropriately mixing the third internal electrondonor compound and the reaction product obtained by the second step inthe presence of an inert organic solvent similar to those mentionedabove in connection with the first step.

In the third step, the third internal electron donor compound may bebrought into contact with the reaction product obtained by the secondstep under arbitrary conditions. Contact/reaction conditions similar tothose employed in the first step may be used.

When bringing the third internal electron donor compound into contactwith the reaction product obtained by the second step to effect areaction, the molar ratio (molar quantity of the third internal electrondonor compound/molar quantity of the magnesium compound) of the thirdinternal electron donor compound to the magnesium compound (that isadded in the first step) is preferably 0.001 to 10, more preferably0.001 to 1, more preferably 0.002 to 1, still more preferably 0.002 to0.6, and yet more preferably 0.003 to 0.6.

When bringing the third internal electron donor compound into contactwith the reaction product obtained by the second step to effect areaction, the molar ratio (molar quantity of the third internal electrondonor compound/molar quantity of the aromatic dicarboxylic diesterrepresented by the general formula (I) (first internal electron donorcompound)) of the third internal electron donor compound to the aromaticdicarboxylic diester represented by the general formula (I) (firstinternal electron donor compound (that is added in the first step) ispreferably 0.01 to 0.9, more preferably 0.01 to 0.6, and still morepreferably 0.02 to 0.4.

When the molar ratio (molar quantity of the third internal electrondonor compound/molar quantity of the aromatic dicarboxylic diesterrepresented by the general formula (I) (first internal electron donorcompound)) of the third internal electron donor compound to the aromaticdicarboxylic diester represented by the general formula (I) (firstinternal electron donor compound) is within the above range, it ispossible to easily suppress a situation in which a large amount of acomplex compound of the third internal electron donor compound and thetetravalent titanium halide compound is formed, and easily improvepolymerization activity and stereoregularity when polymerizing an olefinusing the resulting solid catalyst component.

It is preferable that the molar quantity of the third internal electrondonor compound used in the third step be smaller than the molar quantityof the first internal electron donor compound used in the first step,and equal to or smaller than the molar quantity of the second internalelectron donor compound used in the second step (i.e., molar quantity offirst internal electron donor compound>molar quantity of second internalelectron donor compound≧molar quantity of third internal electron donorcompound).

It is preferable that the total molar quantity of the second internalelectron donor compound used in the second step and the third internalelectron donor compound used in the third step be smaller than the molarquantity of the first internal electron donor compound used in the firststep (i.e., molar quantity of first internal electron donorcompound>(molar quantity of second internal electron donorcompound+molar quantity of third internal electron donor compound)).

The molar ratio (total molar quantity of the second internal electrondonor compound used in the second step and the third internal electrondonor compound used in the third step/molar quantity of the firstinternal electron donor compound used in the first step) of the totalmolar quantity of the second internal electron donor compound used inthe second step and the third internal electron donor compound used inthe third step to the molar quantity of the first internal electrondonor compound used in the first step is preferably 0.02 to 0.95, morepreferably 0.02 to 0.9, and still more preferably 0.02 to 0.8.

When the first internal electron donor compound used in the first stepis the aromatic dicarboxylic diester represented by the general formula(I), the second internal electron donor compound used in the second stepis a carboxylic diester, and the third internal electron donor compoundused in the third step is a carboxylic diester, the total number ofcarbon atoms of the ester residue of the first internal electron donorcompound, the total number of carbon atoms of the ester residue of thesecond internal electron donor compound, and the total number of carbonatoms of the ester residue of the third internal electron donor compoundmay be either identical or different.

An internal electron donor compound in which the number of carbon atomsof the ester residue is small normally exhibits high adhesion to acarrier, and allows particles of a solid catalyst component to easilyaggregate. However, a decrease in polymerization activity tends to occurwhen using a solid catalyst component that supports only an internalelectron donor compound in which the number of carbon atoms of the esterresidue is small.

On the other hand, an internal electron donor compound in which thenumber of carbon atoms of the ester residue is large exhibits lowadhesion to a carrier, but improves polymerization activity. Therefore,it is preferable to preferentially incorporate an internal electrondonor compound in which the number of carbon atoms of the ester residueis large and which exhibits low adhesion to a carrier in the solidcatalyst component, and then bring a small amount of an internalelectron donor compound in which the number of carbon atoms of the esterresidue is small and which exhibits high adhesion to a carrier intocontact with the solid catalyst component (optionally by stepwiseaddition) to effect a reaction, since aggregation of the catalystparticles and a decrease in polymerization activity can be suppressed.

When using an inert organic solvent in the third step, the inert organicsolvent is preferably used in an amount of 0.001 to 500 mol, morepreferably 0.5 to 100 mol, and still more preferably 1.0 to 20 mol,based on 1 mol of the magnesium compound (that is added in the firststep).

When using an inert organic solvent in the third step, it is possible tosuppress interaction between the third internal electron donor compoundand the tetravalent titanium halide compound, and suppress precipitationof a complex compound of the third internal electron donor compound andthe tetravalent titanium halide compound in the solid catalyst componentby reducing the amount of tetravalent titanium halide compound(unreacted tetravalent titanium halide compound) in the inert organicsolvent. Therefore, it is preferable to control the concentration of atetravalent titanium halide compound in the inert organic solvent to 0to 5 mass %, more preferably 0 to 3 mass %, and still more preferably 0to 1 mass %.

Specifically, when implementing the method for producing a solidcatalyst component for olefin polymerization according to one embodimentof the invention, it is desirable to not add a tetravalent titaniumhalide compound to the reaction system in the third step.

When implementing the method for producing a solid catalyst componentfor olefin polymerization according to one embodiment of the invention,it is preferable to add the necessary amount of the magnesium compoundto the reaction system in the first step, and not add the magnesiumcompound to the reaction system in the third step taking account of thereaction efficiency and the like.

In the third step, it is preferable to bring the components into contactwith each other with stirring in a vessel equipped with a stirrer thatcontains an inert gas atmosphere from which water and the like have beenremoved.

After completion of the reaction, it is preferable to wash the reactionproduct after allowing the reaction mixture to stand, appropriatelyremoving the supernatant liquid to achieve a wet state (slurry state),and optionally drying the reaction mixture hot-air drying or the like.

It is preferable to wash the resulting reaction product in the thirdstep after completion of the reaction.

The reaction product is normally washed using a washing agent. Examplesof the washing agent include those mentioned above in connection withthe first step.

The washing temperature, the washing method, the amount of washingagent, the number of washing operations, and the like employed in thethird step are the same as those described above in connection with thefirst step.

According to the method for producing a solid catalyst component forolefin polymerization according to one embodiment of the invention, itis possible to remove unreacted raw material components, reactionby-products (e.g., alkoxytitanium halide and titaniumtetrachloride-carboxylic acid complex), and impurities that remain inthe reaction product by washing the reaction product in the third stepafter bringing the components into contact with each other to effect areaction.

After completion of the reaction, the suspension obtained by washing maybe appropriately allowed to stand, the supernatant liquid may be removedto achieve a wet state (slurry state), and the reaction mixture mayoptionally be dried by hot-air drying or the like.

The product obtained after washing may be used directly as the solidcatalyst component for olefin polymerization. Alternatively, the productmay be brought into contact with a tetravalent titanium halide compound,washed (post-treatment), and used as the solid catalyst component forolefin polymerization. The product may be washed in the same manner asdescribed above.

The resulting solid catalyst component for olefin polymerization may beformed in the shape of particles using a spray dry method that spraysand dries a solution or a suspension using a sprayer. A spherical solidcatalyst component for olefin polymerization having a sharp particlesize distribution can be easily obtained without using a sphericalmagnesium compound in the first step by forming particles using thespray dry method.

It is preferable to add only small amounts of an aluminum compound and asilicon compound to the reaction system in the second step and the thirdstep, or not add an aluminum compound and a silicon compound to thereaction system in the second step and the third step. In particular, itis preferable to not add an organoaluminum compound such as analkylaluminum and an organosilicon compound such as an alkoxysilane tothe reaction system in the second step and the third step.

If the second step and the third step are performed in the presence ofan organoaluminum compound (e.g., alkylaluminum compound oralkylaluminum halide), a reaction in which the internal electron donorcompound supported on the product is removed easily occurs. If thesecond step and the third step are performed in the presence of asilicon compound (e.g., alkoxysilane), adsorption of the internalelectron donor compound and adsorption of the silicon compound compete,and the desired effects may not be obtained.

The method for producing a solid catalyst component for olefinpolymerization according to one embodiment of the invention maypreferably be implemented as described below.

In the first step, a spherical magnesium compound is suspended in aninert organic solvent to prepare a suspension, and the tetravalenttitanium halide compound is brought into contact with the suspension toeffect a reaction. The first internal electron donor compound (i.e., thecompound represented by the general formula (I)) is brought into contactwith the suspension at −20 to 130° C. before or after bringing thetetravalent titanium halide compound into contact with the suspension,and the reaction product is washed with an inert organic solvent toobtain a solid reaction product (a). It is preferable to effect alow-temperature aging reaction before or after bringing the firstinternal electron donor compound (i.e., the compound represented by thegeneral formula (I)) into contact with the suspension.

In the second step, the tetravalent titanium halide compound and thesecond internal electron donor compound are brought into contact withthe reaction product (a) obtained by the first step at 20 to 130° C.(preferably 30 to 120° C., and more preferably 80 to 110° C.) to effecta reaction, and the reaction product is washed with an inert organicsolvent to obtain a solid reaction product (β). The above operation(i.e., contact with the tetravalent titanium halide compound andwashing) may be repeated a plurality of times.

In the third step, the third internal electron donor compound is broughtinto contact with the reaction product (β) obtained by the second stepat 20 to 130° C. (preferably 30 to 120° C., and more preferably 80 to110° C.) in the presence of an inert organic solvent to effect areaction to obtain the target solid catalyst component for olefinpolymerization.

The method for producing a solid catalyst component for olefinpolymerization according to one embodiment of the invention utilizes thearomatic dicarboxylic diester represented by the general formula (I) asthe first internal electron donor compound. Table 1 shows preferablecombinations of the first internal electron donor compound, the secondinternal electron donor compound, and the third internal electron donorcompound.

Specifically, (1) a combination of an aromatic dicarboxylic diester, anaromatic dicarboxylic diester, and an aromatic dicarboxylic diester, (2)a combination of an aromatic dicarboxylic diester, an aromaticdicarboxylic diester, and an ether carbonate, (3) a combination of anaromatic dicarboxylic diester, an alkyl-substituted malonic diester, andan alkyl-substituted malonic diester, (4) a combination of an aromaticdicarboxylic diester, a cycloalkenedicarboxylic diester, and acycloalkenedicarboxylic diester, (5) a combination of an aromaticdicarboxylic diester, a diether, and a diether, and (6) a combination ofan aromatic dicarboxylic diester, a cycloalkanedicarboxylic diester, anda cycloalkanedicarboxylic diester, are preferable as a combination ofthe first internal electron donor compound, the second internal electrondonor compound, and the third internal electron donor compound (seeTable 1).

TABLE 1 First internal electron donor Second internal electron donorThird internal electron donor compound compound compound (1) Aromaticdicarboxylic diester Aromatic dicarboxylic diester Aromatic dicarboxylicdiester (2) Aromatic dicarboxylic diester Aromatic dicarboxylic diesterEther carbonate (3) Aromatic dicarboxylic diester Alkyl-substitutedmalonic diester Alkyl-substituted malonic diester (4) Aromaticdicarboxylic diester Cycloalkenedicarboxylic diesterCycloalkenedicarboxylic diester (5) Aromatic dicarboxylic diesterDiether Diether (6) Aromatic dicarboxylic diesterCycloalkanedicarboxylic diester Cycloalkanedicarboxylic diester

When any of the above combinations (see (1) to (6)) is used as acombination of the first internal electron donor compound, the secondinternal electron donor compound, and the third internal electron donorcompound when implementing the method for producing a solid catalystcomponent for olefin polymerization according to one embodiment of theinvention, it is possible to easily produce an olefin homopolymer orcopolymer that exhibits a high MFR and excellent stereoregularity.

When implementing the method for producing a solid catalyst componentfor olefin polymerization according to one embodiment of the invention,the contact/reaction operation in the first step may be performed in thepresence of a polysiloxane (i.e., third component).

A polysiloxane is a polymer that includes a siloxane linkage (—Si—O—) inthe main chain, and is also referred to as “silicone oil”. Thepolysiloxane may be a chain-like, partially hydrogenated, cyclic, ormodified polysiloxane that is liquid or viscous at room temperature, andhas a viscosity at 25° C. of 0.02 to 100 cm²/s (2 to 10,000 cSt), andpreferably 0.03 to 5 cm²/s (3 to 500 cSt).

Examples of the chain-like polysiloxane include disiloxanes such ashexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane,hexaphenyldisiloxane, 1,3-divinyltetramethyldisiloxane,1,3-dichlorotetramethyldisiloxane, 1,3-dibromotetramethyldisiloxane,chloromethylpentamethyldisiloxane,1,3-bis(chloromethyl)tetramethyldisiloxane, dimethylpolysiloxane, andmethylphenylpolysiloxane. Examples of the partially hydrogenatedpolysiloxane include methyl hydrogen polysiloxane having a degree ofhydrogenation of 10 to 80%. Examples of the cyclic polysiloxane includehexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane,decamethylcyclopentasiloxane, 2,4,6-trimethylcyclotrisiloxane, and2,4,6,8-tetramethylcyclotetrasiloxane. Examples of the modifiedpolysiloxane include a higher fatty acid group-substituteddimethylsiloxane, an epoxy group-substituted dimethylsiloxane, and apolyoxyalkylene group-substituted dimethylsiloxane. Among these,decamethylcyclopentasiloxane and dimethylpolysiloxane are preferable,and decamethylcyclopentasiloxane is particularly preferable.

The magnesium atom content in the solid catalyst component for olefinpolymerization obtained by the production method according to oneembodiment of the invention is preferably 10 to 70 mass %, morepreferably 10 to 50 mass %, more preferably 15 to 40 mass %, andparticularly preferably 15 to 25 mass %.

The titanium atom content in the solid catalyst component for olefinpolymerization obtained by the production method according to oneembodiment of the invention is preferably 0.5 to 8.0 mass %, morepreferably 0.5 to 5.0 mass %, and still more preferably 0.5 to 3.0 mass%.

The halogen atom content in the solid catalyst component for olefinpolymerization obtained by the production method according to oneembodiment of the invention is preferably 20 to 88 mass %, morepreferably 30 to 85 mass %, more preferably 40 to 80 mass %, and stillmore preferably 45 to 75 mass %.

The content of the first internal electron donor compound in the solidcatalyst component for olefin polymerization obtained by the productionmethod according to one embodiment of the invention is preferably 0.1 to30 mass %, more preferably 0.3 to 25 mass %, and particularly preferably0.5 to 20 mass %.

The content of the second internal electron donor compound in the solidcatalyst component for olefin polymerization obtained by the productionmethod according to one embodiment of the invention is preferably 0.1 to30 mass %, more preferably 0.3 to 20 mass %, and particularly preferably0.5 to 10 mass %.

The content of the third internal electron donor compound in the solidcatalyst component for olefin polymerization obtained by the productionmethod according to one embodiment of the invention is preferably 0.1 to30 mass %, more preferably 0.3 to 20 mass %, and particularly preferably0.5 to 10 mass %.

The total content of the first internal electron donor compound, thesecond internal electron donor compound, and the third internal electrondonor compound in the solid catalyst component for olefin polymerizationobtained by the production method according to one embodiment of theinvention is preferably 1.5 to 30 mass %, more preferably 3.0 to 25 mass%, and particularly preferably 6.0 to 25 mass %.

The solid catalyst component for olefin polymerization obtained by theproduction method according to one embodiment of the invention exhibitsits performance in a well-balanced manner when the magnesium atomcontent is 15 to 25 mass %, the titanium atom content is 0.5 to 3.0 mass%, the halogen atom content is 45 to 75 mass %, the content of the firstinternal electron donor compound is 2 to 20 mass %, the content of thesecond internal electron donor compound is 0.3 to 10 mass %, the contentof the third internal electron donor compound is 0.3 to 10 mass %, andthe total content of the first internal electron donor compound, thesecond internal electron donor compound, and the third internal electrondonor compound is 6.0 to 25 mass %, for example.

Note that the magnesium atom content in the solid catalyst componentrefers to a value obtained by dissolving the solid catalyst component ina hydrochloric acid solution, and measuring the magnesium atom contentusing an EDTA titration method that utilizes an EDTA solution.

The titanium atom content in the solid catalyst component refers to avalue measured in accordance with the method (oxidation-reductiontitration) specified in JIS M 8311-1997 (“Method for determination oftitanium in titanium ores”).

The halogen atom content in the solid catalyst component refers to avalue obtained by treating the solid catalyst component using a mixtureof sulfuric acid and purified water to obtain an aqueous solution,preparatively isolating a given amount of the aqueous solution, andtitrating halogen atoms with a silver nitrate standard solution (silvernitrate titration method).

The content of the first internal electron donor compound, the contentof the second internal electron donor compound, the content of the thirdinternal electron donor compound, and the total content of the firstinternal electron donor compound, the second internal electron donorcompound, and the third internal electron donor compound in the solidcatalyst component refer to values measured as described later.

The embodiments of the invention thus provide a method that can easilyproduce a novel solid catalyst component for olefin polymerization thatachieves excellent olefin polymerization activity and activity withrespect to hydrogen during polymerization when homopolymerizing orcopolymerizing an olefin, and can produce an olefin polymer thatexhibits a high MFR, high stereoregularity, and excellent rigidity whileachieving high sustainability of polymerization activity.

Method for Producing Olefin Polymerization Catalyst

An olefin polymerization catalyst according to one embodiment of theinvention is described below.

The olefin polymerization catalyst according to one embodiment of theinvention is produced by bringing the solid catalyst component forolefin polymerization obtained by the production method according to oneembodiment of the invention, an organoaluminum compound represented bythe following general formula (II), and an external electron donorcompound into contact with each other.

R⁴ _(p)AlQ_(3-p)  (II)

wherein R⁴ is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogenatom or a halogen atom, and p is a real number that satisfies 0<p≦3.

The details of the solid catalyst component for olefin polymerizationaccording to one embodiment of the invention have been described above.

R⁴ in the organoaluminum compound represented by the general formula(II) is an alkyl group having 1 to 6 carbon atoms. Specific examples ofthe alkyl group having 1 to 6 carbon atoms represented by R⁴ include amethyl group, an ethyl group, a n-propyl group, an isopropyl group, an-butyl group, an isobutyl group, and the like.

Q in the organoaluminum compound represented by the general formula (II)is a hydrogen atom or a halogen atom. Specific examples of the halogenatom represented by Q include a fluorine atom, a chlorine atom, abromine atom, and an iodine atom.

Specific examples of the organoaluminum compound represented by thegeneral formula (II) include one or more compounds selected fromtriethylaluminum, diethylaluminum chloride, triisobutylaluminum,diethylaluminum bromide, and diethylaluminum hydride. Among these,triethylaluminum and triisobutylaluminum are preferable.

Examples of the external electron donor compound used to produce theolefin polymerization catalyst according to one embodiment of theinvention include organic compounds that include an oxygen atom or anitrogen atom. Examples of the organic compounds that include an oxygenatom or a nitrogen atom include alcohols, phenols, ethers, esters,ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates,and organosilicon compounds. The external electron donor compound may bean organosilicon compound that includes an Si—O—C linkage, anaminosilane compound that includes an Si—N—C linkage, or the like.

Among these, esters such as ethyl benzoate, ethyl p-methoxybenzoate,ethyl p-ethoxybenzoate, methyl p-toluate, ethyl p-toluate, methylanisate, and ethyl anisate, 1,3-diethers, organosilicon compounds thatinclude an Si—O—C linkage, and aminosilane compounds that include anSi—N—C linkage are preferable, and organosilicon compounds that includean Si—O—C linkage, and aminosilane compounds that include an Si—N—Clinkage are particularly preferable.

Examples of the organosilicon compounds that include an Si—O—C linkageand may be used as the external electron donor compound include anorganosilicon compound represented by the following general formula(III).

R⁵Si(OR⁶)_(4-q)  (III)

wherein R⁵ is an alkyl group having 1 to 12 carbon atoms, a cycloalkylgroup having 3 to 12 carbon atoms, a phenyl group, a vinyl group, anallyl group, or an aralkyl group, provided that a plurality of R⁵ areeither identical or different when a plurality of R⁵ are present, R⁶ isan alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3to 6 carbon atoms, a phenyl group, a vinyl group, an allyl group, or anaralkyl group, provided that a plurality of R⁶ are either identical ordifferent when a plurality of R⁶ are present, and q is an integer from 0to 3.

Examples of the aminosilane compounds that include an Si—N—C linkage andmay be used as the external electron donor compound include anorganosilicon compound represented by the following general formula(IV).

(R⁷R⁸N)_(s)SiR⁹ _(4-s)  (IV)

wherein R⁷ and R⁸ are a hydrogen atom, a linear alkyl group having 1 to20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, avinyl group, an allyl group, an aralkyl group, a cycloalkyl group having3 to 20 carbon atoms, or an aryl group, provided that R⁷ and R⁸ areeither identical or different, and optionally bond to each other to forma ring, R⁹ is a linear alkyl group having 1 to 20 carbon atoms, abranched alkyl group having 3 to 20 carbon atoms, a vinyl group, anallyl group, an aralkyl group, a linear or branched alkoxy group having1 to 20 carbon atoms, a vinyloxy group, an allyloxy group, a cycloalkylgroup having 3 to 20 carbon atoms, an aryl group, or an aryloxy group,provided that a plurality of R⁹ are either identical or different when aplurality of R⁹ are present, and s is an integer from 1 to 3.

Examples of the organosilicon compound represented by the generalformula (III) or (IV) include phenylalkoxysilanes, alkylalkoxysilanes,phenylalkylalkoxysilanes, cycloalkylalkoxysilanes,alkyl(cycloalkyl)alkoxysilanes, (alkylamino)alkoxysilanes,alkyl(alkylamino)alkoxysilanes, cycloalkyl(alkylamino)alkoxysilanes,tetraalkoxysilanes, tetrakis(alkylamino)silanes,alkyltris(alkylamino)silanes, dialkylbis(alkylamino)silanes,trialkyl(alkylamino)silanes, and the like. Specific examples of theorganosilicon compound represented by the general formula (III) or (IV)include n-propyltriethoxysilane, cyclopentyltriethoxysilane,phenyltrimethoxysilane, phenyltriethoxysilane, t-butyltrimethoxysilane,diisopropyldimethoxysilane, isopropylisobutyldimethoxysilane,diisopentyldimethoxysilane, bis(2-ethylhexyl)dimethoxysilane,t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane,dicyclopentyldimethoxysilane, dicyclohexyldimetoxysilane,cyclohexylcyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane,tetraethoxysilane, tetrabutoxysilane, bis(ethylamino)methylethylsilane,bis(ethylamino)-t-butylmethylsilane, bis(ethylamino)dicyclohexylsilane,dicyclopentylbis(ethylamino)silane,bis(methylamino)(methylcyclopentylamino)methylsilane,diethylaminotriethoxysilane, bis(cyclohexylamino)dimethoxysilane,bis(perhydroisoquinolino)dimethoxysilane,bis(perhydroquinolino)dimethoxysilane,ethyl(isoquinolino)dimethoxysilane, and the like. For example, one ormore compounds selected from n-propyltriethoxysilane,phenyltrimethoxysilane, t-butylmethyldimethoxysilane,t-butylethyldimethoxysilane, diisopropyldimethoxysilane,isopropylisobutyldimethoxysilane, diisopentyldimethoxysilane,diphenyldimethoxysilane, dicyclopentyldimethoxysilane,cyclohexylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane,t-butylmethylbis(ethylamino)silane, bis(ethylamino)dicyclohexylsilane,dicyclopentylbis(ethylamino)silane,bis(perhydroisoquinolino)dimethoxysilane, diethylaminotriethoxysilane,and the like may be used.

The solid catalyst component for olefin polymerization obtained by theproduction method according to one embodiment of the invention, theorganoaluminum compound, and the external electron donor compound may beused to produce the olefin polymerization catalyst according to oneembodiment of the invention in an arbitrary ratio as long as theadvantageous effects of the invention can be achieved. Theorganoaluminum compound is preferably used in an amount of 1 to 2000mol, and more preferably 50 to 1000 mol, per mol of the titanium atomsincluded in the solid catalyst component for olefin polymerizationobtained by the production method according to one embodiment of theinvention. The external electron donor compound is preferably used in anamount of 0.002 to 10 mol, more preferably 0.01 to 2 mol, and still morepreferably 0.01 to 0.5 mol, per mol of the organoaluminum compound.

The olefin polymerization catalyst according to one embodiment of theinvention may be produced by bringing (α) the solid catalyst componentfor olefin polymerization obtained by the production method according toone embodiment of the invention, (β) the organoaluminum compound, and(γ) the external electron donor compound into contact with each otherusing a known method.

The components may be brought into contact with each other in anarbitrary order. For example, the components may be brought into contactwith each other in any of the orders shown below.

(i) Solid catalyst component (a)→external electron donor compound(γ)→organoaluminum compound (β)(ii) Organoaluminum compound (β)→external electron donor compound(γ)→solid catalyst component (α)(iii) External electron donor compound (γ)→solid catalyst component(α)→organoaluminum compound (β)(iv) External electron donor compound (γ)→organoaluminum compound(β)→solid catalyst component (α)

It is preferable to bring the components into contact with each otheraccording to the contact order example (ii).

Note that the symbol “→” in the contact order examples (i) to (iv)indicates the contact order. For example, “solid catalyst component(α)→organoaluminum compound (β)→external electron donor compound (γ)”means that the organoaluminum compound (β) is brought into contact with(added to) the solid catalyst component (α), and the external electrondonor (γ) is brought into contact with the mixture.

The olefin polymerization catalyst according to one embodiment of theinvention may be produced by bringing the solid catalyst component forolefin polymerization according to one embodiment of the invention, theorgano aluminum compound, and the external electron donor compound intocontact with each other in the absence of an olefin, or may be producedby bringing the solid catalyst component for olefin polymerizationaccording to one embodiment of the invention, the organoaluminumcompound, and the external electron donor compound into contact witheach other in the presence of an olefin (i.e., in the polymerizationsystem).

The embodiments of the invention thus provide a novel olefinpolymerization catalyst that achieves excellent olefin polymerizationactivity and activity with respect to hydrogen during polymerizationwhen homopolymerizing or copolymerizing an olefin, and can produce anolefin polymer that exhibits a high MFR, high stereoregularity, andexcellent rigidity while achieving high sustainability of polymerizationactivity.

A method for producing an olefin polymer according to one embodiment ofthe invention is described below.

The method for producing an olefin polymer according to one embodimentof the invention includes polymerizing an olefin in the presence of theolefin polymerization catalyst according to one embodiment of theinvention.

The olefin that is polymerized using the method for producing an olefinpolymer according to one embodiment of the invention may be one or moreolefins selected from ethylene, propylene, 1-butene, 1-pentene,4-methyl-1-pentene, vinylcyclohexane, and the like. Among these,ethylene, propylene, and 1-butene are preferable, and propylene is morepreferable.

Propylene may be copolymerized with another olefin. It is preferable tosubject propylene and another α-olefin to block copolymerization. Ablock copolymer obtained by block copolymerization is a polymer thatincludes two or more segments in which the monomer composition changessequentially. A block copolymer obtained by block copolymerization has astructure in which two or more polymer chains (segments) that differ inpolymer primary structure (e.g., type of monomer, type of comonomer,comonomer composition, comonomer content, comonomer arrangement, andstereoregularity) are linked within one molecular chain.

The olefin that is copolymerized with propylene is preferably anα-olefin having 2 to 20 carbon atoms (excluding propylene having 3carbon atoms). Specific examples of the olefin include ethylene,1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, and the like.These olefins may be used either alone or in combination. Among these,ethylene and 1-butene are preferable.

The olefin may be polymerized using the method for producing an olefinpolymer according to one embodiment of the invention in the presence orabsence of an organic solvent.

The olefin may be used in a gaseous state or a liquid state.

The olefin is polymerized in a reactor (e.g., autoclave) in the presenceof the olefin polymerization catalyst according to one embodiment of theinvention with heating and pressurizing, for example.

When implementing the method for producing an olefin polymer accordingto one embodiment of the invention, the polymerization temperature isnormally 200° C. or less, preferably 100° C. or less. The polymerizationtemperature is preferably 60 to 100° C., and more preferably 70 to 90°C., from the viewpoint of improving activity and stereoregularity. Whenimplementing the method for producing an olefin polymer according to oneembodiment of the invention, the polymerization pressure is preferably10 MPa or less, and more preferably 5 MPa or less.

A continuous polymerization method or a batch polymerization method maybe used. The olefin may be polymerized in a single step, or may bepolymerized in two or more steps.

When implementing the method for producing an olefin polymer accordingto one embodiment of the invention, block copolymerization of propyleneand another olefin may normally be effected by polymerizing propylene,or copolymerizing propylene and a small amount of α-olefin (e.g.,ethylene) in the first step, and copolymerizing propylene and anα-olefin (e.g., ethylene) in the second step in the presence of theolefin polymerization catalyst according to one embodiment of theinvention. Note that the first-step polymerization reaction may berepeatedly effected a plurality of times, and the second-steppolymerization reaction may be repeatedly effected a plurality of times(i.e., multistep reaction). An olefin monomer such as propylene may beused in a gaseous state or a liquid state.

More specifically, block copolymerization of propylene and anotherolefin may be effected by effecting first-step polymerization whileadjusting the polymerization temperature and the polymerization time sothat the resulting polypropylene part accounts for 20 to 90 wt % of thefinal copolymer, introducing propylene and ethylene or another α-olefinin the second step, and polymerizing the components so that the rubberpart (e.g., ethylene-propylene rubber (EPR)) accounts for 10 to 80 wt %of the final copolymer.

The polymerization temperature in the first step and the second step ispreferably 200° C. or less, and more preferably 100° C. or less. Thepolymerization pressure in the first step and the second step ispreferably 10 MPa or less, and more preferably 5 MPa or less.

The copolymerization reaction may be effected using a continuouspolymerization method or a batch polymerization method. Thepolymerization reaction may be effected in one step, or may be effectedin two or more steps.

The polymerization time (i.e., the residence time in the reactor) ineach polymerization step, or the polymerization time when using acontinuous polymerization method, is preferably 1 minute to 5 hours.

Examples of the polymerization method include a slurry polymerizationmethod that utilizes an inert hydrocarbon solvent such as cyclohexane orheptane, a bulk polymerization method that utilizes a solvent such asliquefied propylene, and a vapor-phase polymerization method in which asolvent is not substantially used. Among these, a bulk polymerizationmethod and a vapor-phase polymerization method are preferable. It ispreferable to use a vapor-phase polymerization method in the second stepin order to suppress elution from the polypropylene (PP) particlesincluded in EPR.

When implementing the method for producing an olefin polymer accordingto one embodiment of the invention, preliminary polymerization may beeffected by bringing part or all of the components of the olefinpolymerization catalyst according to one embodiment of the inventioninto contact with the olefin before polymerizing the olefin (hereinaftermay be appropriately referred to as “main polymerization”).

The components of the olefin polymerization catalyst according to oneembodiment of the invention may be brought into contact with the olefinin an arbitrary order when effecting the preliminary polymerization. Itis preferable to add the organoaluminum compound to a preliminarypolymerization system that contains an inert gas atmosphere or an olefingas atmosphere, add the solid catalyst component for olefinpolymerization according to one embodiment of the invention to thepreliminary polymerization system, and bring one or more olefins (e.g.,propylene) into contact with the mixture. It is also preferable to addthe organoaluminum compound to a preliminary polymerization system thatcontains an inert gas atmosphere or an olefin gas atmosphere, add theexternal electron donor compound to the preliminary polymerizationsystem, add the solid catalyst component for olefin polymerizationaccording to one embodiment of the invention to the preliminarypolymerization system, and bring one or more olefins (e.g., propylene)into contact with the mixture.

The olefin subjected to the main polymerization, or a monomer such asstyrene may be used for the preliminary polymerization. The preliminarypolymerization conditions may be the same as the above polymerizationconditions.

It is possible to improve the catalytic activity, and easily improve thestereoregularity, the particle properties, and the like of the resultingpolymer by effecting the preliminary polymerization.

The embodiments of the invention thus provide a novel method that canproduce an olefin polymer that exhibits a high MFR, highstereoregularity, and excellent rigidity while achieving highsustainability of polymerization activity.

The invention is further described below by way of examples. Note thatthe following examples are for illustration purposes only, and theinvention is not limited to the following examples.

In the examples and comparative examples, the sphericity of thedialkoxymagnesium particles, and the content of magnesium atoms,titanium atoms, halogen atoms, and the internal electron donor compoundin the solid catalyst component were measured as described below.

Sphericity of Dialkoxymagnesium Particles

The sphericity of the dialkoxymagnesium particles was determined byphotographing the dialkoxymagnesium particles using a scanning electronmicroscope (“JSM-7500F” manufactured by JEOL Ltd.) at a magnification atwhich 500 to 1000 dialkoxymagnesium particles were displayed on ascreen, randomly sampling 500 or more dialkoxymagnesium particles fromthe photographed dialkoxymagnesium particles, determining the area S andthe circumferential length L of each dialkoxymagnesium particle usingimage analysis software (“MacView Ver. 4.0” manufactured by MOUNTECHCo., Ltd.), calculating the sphericity of each dialkoxymagnesiumparticle using the following expression, and calculating the arithmeticmean value.

Sphericity of each dialkoxymagnesium particle=4π×S÷L ²

Content of Magnesium Atoms in Solid Catalyst Component

The solid catalyst component from which the solvent component had beencompletely removed by heating (drying) under reduced pressure wasweighed, and dissolved in a hydrochloric acid solution. After theaddition of methyl orange (indicator) and a saturated ammonium chloridesolution, the mixture was neutralized with aqueous ammonia, heated,cooled, and filtered to remove a precipitate (titanium hydroxide). Agiven amount of the filtrate was isolated preparatively, and heated.After the addition of a buffer and an EBT mixed indicator, magnesiumatoms were titrated using an EDTA solution to determine the content ofmagnesium atoms in the solid catalyst component (EDTA titration method).

Content of Titanium Atoms in Solid Catalyst Component

The content of titanium atoms in the solid catalyst component wasdetermined in accordance with the method (oxidation-reduction titration)specified in JIS M 8311-1997 (“Method for determination of titanium intitanium ores”).

Content of Halogen Atoms in Solid Catalyst Component

The solid catalyst component from which the solvent component had beencompletely removed by heating (drying) under reduced pressure wasweighed, and treated with a mixture of sulfuric acid and purified waterto obtain an aqueous solution. A given amount of the aqueous solutionwas isolated preparatively, and halogen atoms were titrated with asilver nitrate standard solution using an automatic titration device(“COM-1500” manufactured by Hiranuma Sangyo Co., Ltd.) to determine thecontent of halogen atoms in the solid catalyst component (silver nitratetitration method).

Content of Internal Electron Donor Compound in Solid Catalyst Component

The content of the internal electron donor compound (first internalelectron donor compound, second internal electron donor compound, andthird internal electron donor compound) in the solid catalyst componentwas determined using a gas chromatograph (“GC-14B” manufactured byShimadzu Corporation) under the following conditions. The number ofmoles of each component (each internal electron donor compound) wascalculated from the gas chromatography measurement results using acalibration curve that was drawn in advance using the measurementresults at a known concentration.

Measurement Conditions

Column: packed column (2.6 mm (diameter)×2.1 m, Silicone SE-30 10%,Chromosorb WAW DMCS 80/100, manufactured by GL Sciences Ltd.)Detector: flame ionization detector (FID)Carrier gas: helium, flow rate: 40 ml/minMeasurement temperature: vaporization chamber: 280° C., column: 225° C.,detector: 280° C., or vaporization chamber: 265° C., column: 180° C.,detector: 265° C.

Example 1 Production of Solid Catalyst Component (1) First Step

A 500 ml round bottom flask equipped with a stirrer in which theinternal atmosphere had been sufficiently replaced by nitrogen gas, wascharged with 40 ml (364 mmol) of titanium tetrachloride and 60 ml (565mmol) of toluene to prepare a solution.

A suspension prepared using 20 g (175 mmol) of sphericaldiethoxymagnesium (sphericity, 1.10), 80 ml (753 mmol) of toluene, and1.8 ml (7.8 mmol) of di-n-propyl phthalate was added to the solution.The mixture was stirred at −5° C. for 1 hour, and heated to 110° C. 3.6ml (15.5 mmol) of di-n-propyl phthalate was added stepwise to themixture while heating the mixture. After reacting the mixture at 110° C.for 2 hours with stirring, the reaction mixture was allowed to stand,and the supernatant liquid was removed to obtain a reaction productslurry.

After the addition of 187 ml of toluene (100° C.) to the reactionproduct slurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated four timesto wash the reaction product to obtain a reaction product slurryincluding a solid component (I).

(2) Second Step

170 ml (1600 mmol) of toluene and 30 ml (273 mmol) of titaniumtetrachloride were added to the reaction product slurry including thesolid component (I). The mixture was heated to 110° C., and reacted for2 hours with stirring. After completion of the reaction, the supernatantliquid (toluene) was removed. After the addition of 180 ml of tolueneand 20 ml (182 mmol) of titanium tetrachloride, the mixture was heatedto 80° C. After the addition of 0.5 ml (2.2 mmol) of di-n-propylphthalate, the mixture was heated to 110° C., and reacted for 2 hourswith stirring. The resulting reaction mixture was allowed to stand, andthe supernatant liquid was removed to obtain a reaction product slurry.

After completion of the reaction, 187 ml of toluene (100° C.) was addedto the reaction product slurry, the mixture was stirred and allowed tostand, and the supernatant liquid was removed. This operation wasrepeated twice. After the addition of 150 ml of n-heptane (60° C.), themixture was stirred and allowed to stand, and the supernatant liquid wasremoved. This operation was repeated five times to wash the reactionproduct to obtain a reaction product slurry including a solid component(II).

(3) Third Step

150 ml (1024 mmol) of heptane was added to the reaction product slurryincluding the solid component (II) to adjust the concentration oftitanium tetrachloride in the reaction mixture to 0.2 mass %, and themixture was heated to 80° C. After the addition of 0.5 ml (2.5 mmol) ofdiethyl phthalate, the mixture was reacted at 80° C. for 1 hour withstirring. The resulting reaction mixture was allowed to stand, and thesupernatant liquid was removed to obtain a reaction product slurry.

After the addition of 150 ml of n-heptane (60° C.) to the reactionproduct slurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated twice towash the reaction product to obtain about 20 g of a solid catalystcomponent (A1) for olefin polymerization.

The solid catalyst component (A1) had a magnesium atom content of 18.6mass %, a titanium atom content of 1.5 mass %, a halogen atom content of60.8 mass %, and a total phthalic diester content of 15.5 mass %.

Preparation of Propylene Polymerization Catalyst and Polymerization ofPropylene

An autoclave (internal volume: 2.0 l) equipped with a stirrer in whichthe internal atmosphere had been completely replaced by nitrogen gas,was charged with 1.32 mmol of triethylaluminum, 0.13 mmol ofdicyclopentyldimethoxysilane (DCPDMS), and the solid catalyst component(A1) (0.0013 mmol on a titanium atom basis) to prepare an olefinpolymerization catalyst.

The autoclave was charged with 9.0 l of hydrogen gas and 1.4 l ofliquefied propylene. The liquefied propylene was subjected topreliminary polymerization at 20° C. for 5 minutes under a pressure of1.1 MPa, heated, and polymerized at 70° C. for 1 hour under a pressureof 3.5 MPa to obtain a propylene polymer (polypropylene).

The polymerization activity per gram of the solid catalyst component,the p-xylene-soluble content (XS) in the resulting polymer, the meltflow rate (MFR) of the polymer, the molecular weight distribution(Mw/Mn) of the polymer, the flexural modulus (FM) of the polymer, andthe isotactic pentad fraction (NMR-mmmm) of the polymer were measured asdescribed below. The results are shown in Table 2.

Polymerization Activity

The polymerization activity per gram of the solid catalyst component wascalculated using the following expression.

Polymerization activity (g-pp/g-catalyst)=mass (g) of polymer/mass (g)of solid catalyst component included in olefin polymerization catalyst

Xylene-Soluble Content (XS) in Polymer

A flask equipped with a stirrer was charged with 4.0 g of the polymer(polypropylene) and 200 ml of p-xylene. The external temperature wasincreased to be equal to or higher than the boiling point (about 150°C.) of xylene, and the polymer was dissolved over 2 hours whilemaintaining p-xylene contained in the flask at a temperature (137 to138° C.) lower than the boiling point. The solution was cooled to 23° C.over 1 hour, and an insoluble component and a soluble component wereseparated by filtration. A solution of the soluble component wascollected, and p-xylene was evaporated by heating (drying) under reducedpressure. The weight of the residue was calculated, and the relativeratio (mass %) with respect to the polymer (propylene) was calculated todetermine the xylene-soluble content (XS).

Melt Flow Rate (MFR) of Polymer

The melt flow rate (MFR) (melt flow index) (g/10 min) of the polymer wasmeasured in accordance with ASTM D 1238 (JIS K 7210).

Molecular Weight Distribution (Mw/Mn) of Polymer

The molecular weight distribution (weight average molecular weight(Mw)/number average molecular weight (Mn)) of the polymer was determinedusing a GPC device (“GPC 2000” manufactured by Waters) under thefollowing conditions.

Solvent: o-dichlorobenzene (ODCB)Flow rate: 1 mg/min

Column: Shodex UT-806M×3 and HT-803×1

Sample concentration: 1 mg/ml

Flexural Modulus (FM) of Polymer

The polymer was injection-molded to prepare a property measurementspecimen in accordance with JIS K 7171. The specimen was conditioned ina temperature-controlled room maintained at 23° C. for 144 hours ormore, and the flexural modulus (FM) (MPa) was measured using thespecimen provided that a liquid/powder exudate was not observed on thesurface thereof.

Isotactic Pentad Fraction (NMR-mmmm) of Polymer

The term “isotactic pentad fraction (NMR-mmmm)” refers to the fraction(%) of a propylene monomer unit situated at the center of an isotacticchain (i.e., a chain in which five propylene monomer units aresequentially meso-linked) of a pentad unit in a polypropylene molecularchain that is measured by the method described in A. Zambelli et al,Macromolecules, 6, 925 (1973). The isotactic pentad fraction (NMR-mmmm)is calculated using ¹³C-NMR. The area fraction of the mmmm peak withrespect to the total absorption peaks in the methyl-carbon region of the¹³C-NMR spectrum was calculated, and taken as the isotactic pentadfraction.

The isotactic pentad fraction (NMR-mmmm) of the polymer was determinedby performing ¹³C-NMR measurement using an NMR device (“JNM-ECA400”manufactured by JEOL Ltd.) under the following conditions.

¹³C-NMR Conditions

Measurement mode: proton decoupling methodPulse width: 7.25 μsecPulse repetition time: 7.4 secIntegration count: 10,000Solvent: tetrachloroethane-d2Sample concentration: 200 mg/3.0 ml

Example 2 Production of Solid Catalyst Component (1) First Step

A 500 ml round bottom flask equipped with a stirrer in which theinternal atmosphere had been sufficiently replaced by nitrogen gas, wascharged with 40 ml (364 mmol) of titanium tetrachloride and 60 ml (565mmol) of toluene to prepare a solution.

A suspension prepared using 20 g (175 mmol) of sphericaldiethoxymagnesium (sphericity (l/w): 1.10), 80 ml (753 mmol) of toluene,and 1.8 ml (7.8 mmol) of di-n-propyl phthalate was added to thesolution. The mixture was stirred at −5° C. for 1 hour, and heated to110° C. 3.6 ml (15.5 mmol) of di-n-propyl phthalate was added stepwiseto the mixture while heating the mixture. After reacting the mixture at110° C. for 2 hours with stirring, the reaction mixture was allowed tostand, and the supernatant liquid was removed to obtain a reactionproduct slurry including a solid component (I).

After the addition of 187 ml of toluene (100° C.) to the reactionproduct slurry including the solid component (I), the mixture wasstirred and allowed to stand, and the supernatant liquid was removed.This operation was repeated four times to wash the reaction product.

(2) Second Step

170 ml (1600 mmol) of toluene and 30 ml (273 mmol) of titaniumtetrachloride were added to the reaction product slurry including thesolid component (I). The mixture was heated to 110° C., and reacted for2 hours with stirring. After completion of the reaction, the supernatantliquid (toluene) was removed. After the addition of 180 ml of tolueneand 20 ml (182 mmol) of titanium tetrachloride, the mixture was heatedto 80° C. After the addition of 0.5 ml (2.2 mmol) of di-n-propylphthalate, the mixture was heated to 110° C., and reacted for 2 hourswith stirring. The resulting reaction mixture was allowed to stand, andthe supernatant liquid was removed to obtain a reaction product slurry.

After the addition of 187 ml of toluene (100° C.) to the reactionproduct slurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated twice towash the reaction product to obtain a reaction product slurry includinga solid component (II).

(3) Third Step

187 ml (1760 mmol) of toluene was added to the reaction product slurryincluding the solid component (II) to adjust the concentration oftitanium tetrachloride in the reaction mixture to 1.3 mass %, and themixture was heated to 80° C. After the addition of 0.5 ml (2.5 mmol) ofdiethyl phthalate, the mixture was heated to 100° C., and reacted for 1hour with stirring. The resulting reaction mixture was allowed to stand,and the supernatant liquid was removed to obtain a reaction productslurry.

After the addition of 150 ml of n-heptane (60° C.) to the reactionproduct slurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated seven timesto wash the reaction product to obtain about 20 g of a solid catalystcomponent (A2) for olefin polymerization. The solid catalyst component(A2) had a magnesium atom content of 19.9 mass %, a titanium atomcontent of 1.2 mass %, a halogen atom content of 61.3 mass %, and atotal phthalic diester content of 16.8 mass %.

Preparation of Polymerization Catalyst and Polymerization of Propylene

A polymerization catalyst was prepared, and propylene was polymerized inthe same manner as in Example 1, except that the resulting solidcatalyst component (A2) was used, and the polymerization activity andthe resulting polymer were evaluated. The results are shown in Table 2.

Example 3

A solid catalyst component (A2) was produced in the same manner as inExample 2. A polymerization catalyst was prepared, and propylene waspolymerized in the same manner as in Example 2, except that 0.13 mmol ofdiisopropyl dimethoxysilane (DIPDMS) was used instead of 0.13 mmol ofdicyclopentyldimethoxysilane (DCPDMS), and the polymerization activityand the resulting polymer were evaluated. The results are shown in Table2.

Example 4

A solid catalyst component (A2) was produced in the same manner as inExample 2. A polymerization catalyst was prepared, and propylene waspolymerized in the same manner as in Example 2, except that 0.13 mmol ofdicyclopentylbis(ethylamino)silane (DCPEAS) was used instead of 0.13mmol of dicyclopentyldimethoxysilane (DCPDMS), and the amount ofhydrogen gas was changed from 9.01 to 6.0 l, and the polymerizationactivity and the resulting polymer were evaluated. The results are shownin Table 2.

Example 5

A solid catalyst component (A2) was produced in the same manner as inExample 2. A polymerization catalyst was prepared, and propylene waspolymerized in the same manner as in Example 2, except that 0.13 mmol ofdiethylaminotriethoxysilane (DEATES) was used instead of 0.13 mmol ofdicyclopentyldimethoxysilane (DCPDMS), and the amount of hydrogen gaswas changed from 9.01 to 6.0 l, and the polymerization activity and theresulting polymer were evaluated. The results are shown in Table 2.

Example 6

A solid catalyst component (A2) was produced in the same manner as inExample 2. A polymerization catalyst was prepared, and propylene waspolymerized in the same manner as in Example 2, except that 0.13 mmol ofa mixture prepared by mixing dicyclopentyldimethoxysilane andn-propyltriethoxysilane in a ratio of 5:95 (mol/mol) was used instead of0.13 mmol of dicyclopentyldimethoxysilane (DCPDMS), and the amount ofhydrogen gas was changed from 9.01 to 6.0 l, and the polymerizationactivity and the resulting polymer were evaluated. The results are shownin Table 2.

Example 7

A solid catalyst component (A3) was produced in the same manner as inExample 2, except that 0.5 ml (2.2 mmol) of di-n-propyl phthalate wasused in the third step (see (3)) instead of 0.5 ml (2.5 mmol) of diethylphthalate.

The solid catalyst component (A3) had a magnesium atom content of 19.4mass %, a titanium atom content of 1.3 mass %, a halogen atom content of61.5 mass %, and a total phthalic diester content of 16.7 mass %.

A polymerization catalyst was prepared, and propylene was polymerized inthe same manner as in Example 2, except that the solid catalystcomponent (A3) was used instead of the solid catalyst component (A2),and the polymerization activity and the resulting polymer wereevaluated. The results are shown in Table 2.

Example 8

A solid catalyst component (A4) was produced in the same manner as inExample 2, except that 0.5 ml (2.5 mmol) of diethyl phthalate was usedin the second step (see (2)) instead of 0.5 ml (2.2 mmol) of di-n-propylphthalate.

The solid catalyst component (A4) had a magnesium atom content of 19.8mass %, a titanium atom content of 1.3 mass %, a halogen atom content of60.7 mass %, and a total phthalic diester content of 16.9 mass %.

A polymerization catalyst was prepared, and propylene was polymerized inthe same manner as in Example 2, except that the solid catalystcomponent (A4) was used instead of the solid catalyst component (A2),and the polymerization activity and the resulting polymer wereevaluated. The results are shown in Table 2.

Example 9

A solid catalyst component (A5) was produced in the same manner as inExample 2, except that 0.5 ml (2.0 mmol) of dimethyl diisobutylmalonatewas used in the third step (see (3)) instead of 0.5 ml (2.5 mmol) ofdiethyl phthalate.

The solid catalyst component (A5) had a magnesium atom content of 19.3mass %, a titanium atom content of 1.4 mass %, a halogen atom content of62.0 mass %, and a total content of the phthalic diester and thediisobutylmalonic diester of 16.3 mass %.

A polymerization catalyst was prepared, and propylene was polymerized inthe same manner as in Example 2, except that the solid catalystcomponent (A5) was used instead of the solid catalyst component (A2),and the polymerization activity and the resulting polymer wereevaluated. The results are shown in Table 2.

Example 10

A solid catalyst component (A6) was produced in the same manner as inExample 2, except that 0.5 ml (2.0 mmol) of dimethyl diisobutylmalonatewas used in the second step (see (2)) instead of 0.5 ml (2.2 mmol) ofdi-n-propyl phthalate, and 0.5 ml (2.0 mmol) of dimethyldiisobutylmalonate was used in the third step (see (3)) instead of 0.5ml (2.5 mmol) of diethyl phthalate.

The solid catalyst component (A6) had a magnesium atom content of 19.8mass %, a titanium atom content of 1.2 mass %, a halogen atom content of61.1 mass %, and a total content of the phthalic diester and thediisobutylmalonic diester of 16.5 mass %.

A polymerization catalyst was prepared, and propylene was polymerized inthe same manner as in Example 2, except that the solid catalystcomponent (A6) was used instead of the solid catalyst component (A2),and the polymerization activity and the resulting polymer wereevaluated. The results are shown in Table 2.

Example 11

A solid catalyst component (A7) was produced in the same manner as inExample 2, except that 0.5 ml (3.0 mmol) of diethyl succinate was usedin the third step (see (3)) instead of 0.5 ml (2.5 mmol) of diethylphthalate.

The solid catalyst component (A7) had a magnesium atom content of 19.4mass %, a titanium atom content of 1.5 mass %, a halogen atom content of62.2 mass %, and a total content of the phthalic diester and thesuccinic diester of 16.2 mass %.

A polymerization catalyst was prepared, and propylene was polymerized inthe same manner as in Example 2, except that the solid catalystcomponent (A7) was used instead of the solid catalyst component (A2),and the polymerization activity and the resulting polymer wereevaluated. The results are shown in Table 2.

Example 12

A solid catalyst component (A8) was produced in the same manner as inExample 2, except that 0.5 ml (3.1 mmol) of diethyl maleate was used inthe third step (see (3)) instead of 0.5 ml (2.5 mmol) of diethylphthalate.

The solid catalyst component (A8) had a magnesium atom content of 19.0mass %, a titanium atom content of 1.5 mass %, a halogen atom content of62.4 mass %, and a total content of the phthalic diester and the maleicdiester of 17.0 mass %.

A polymerization catalyst was prepared, and propylene was polymerized inthe same manner as in Example 2, except that the solid catalystcomponent (A8) was used instead of the solid catalyst component (A2),and the polymerization activity and the resulting polymer wereevaluated. The results are shown in Table 2.

Example 13

A solid catalyst component (A9) was produced in the same manner as inExample 2, except that 0.5 ml (2.3 mmol) of diethylcyclohexane-1,2-carboxylate (trans isomer: 33%) was used in the thirdstep (see (3)) instead of 0.5 ml (2.5 mmol) of diethyl phthalate.

The solid catalyst component (A9) had a magnesium atom content of 19.0mass %, a titanium atom content of 1.6 mass %, a halogen atom content of62.6 mass %, and a total content of the phthalic diester and thecyclohexane-1,2-carboxylic diester of 16.2 mass %.

A polymerization catalyst was prepared, and propylene was polymerized inthe same manner as in Example 2, except that the solid catalystcomponent (A9) was used instead of the solid catalyst component (A2),and the polymerization activity and the resulting polymer wereevaluated. The results are shown in Table 2.

Example 14 Production of Solid Catalyst Component (1) First Step

A 500 ml round-bottom flask equipped with a stirrer in which theinternal atmosphere had been sufficiently replaced by nitrogen gas, wascharged with 120 ml (819 mmol) of n-heptane. After the addition of 15 g(158 mmol) of anhydrous magnesium chloride and 106 ml (274 mmol) oftetrabutoxytitanium, the mixture was reacted at 90° C. for 1.5 hours toobtain a homogenous solution. After cooling the solution to 40° C., 24ml (88 mmol) of methyl hydrogen polysiloxane (20 cSt) was added to thesolution, and a precipitation reaction was effected for 5 hours. Theresulting reaction mixture was allowed to stand, the supernatant liquidwas removed to obtain a reaction product slurry, and the reactionproduct was sufficiently washed with n-heptane.

A 500 ml round-bottom flask equipped with a stirrer in which theinternal atmosphere had been sufficiently replaced by nitrogen gas, wascharged with 40 g of the reaction product, and n-heptane was added tothe flask so that the concentration of the reaction product was 200mg/ml. After the addition of 12 ml (105 mmol) of SiCl₄, the mixture wasreacted at 90° C. for 3 hours. The resulting reaction mixture wasallowed to stand, the supernatant liquid was removed to obtain areaction product slurry, and the reaction product was sufficientlywashed with n-heptane.

After the addition of n-heptane so that the concentration of thereaction product was 100 mg/ml, 20 ml (182 mmol) of TiCl₄ was added tothe mixture. After the addition of 7.2 ml (27.1 mmol) of di-n-butylphthalate, the mixture was reacted at 95° C. for 3 hours. The resultingreaction mixture was allowed to stand, and the supernatant liquid wasremoved to obtain a reaction product slurry.

After the addition of 120 ml of n-heptane to the reaction productslurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated seven timesto wash the reaction product to obtain a reaction product slurryincluding a solid component (I).

(2) Second Step

100 ml (683 mmol) of n-heptane and 20 ml (182 mmol) of titaniumtetrachloride were added to the reaction product slurry including thesolid component (I). The mixture was heated to 100° C., and reacted for2 hours with stirring. After completion of the reaction, the supernatantliquid (toluene) was removed, followed by the addition of 100 ml ofn-heptane. After the addition of 20 ml of titanium tetrachloride, 1.0 ml(4.3 mmol) of di-n-propyl phthalate was added to the mixture, and themixture was reacted at 95° C. for 3 hours. The resulting reactionmixture was allowed to stand, and the supernatant liquid was removed toobtain a reaction product slurry.

After treating the reaction product slurry with 100 ml of heptane underreflux, the mixture was allowed to stand, and the supernatant liquid wasremoved. This operation was repeated twice to wash the reaction productto obtain a reaction product slurry including a solid component (II).

(3) Third Step

187 ml (1760 mmol) of toluene was added to the reaction product slurryincluding the solid component (II) to adjust the concentration oftitanium tetrachloride in the reaction mixture to 2.5 mass %, and themixture was heated to 80° C. After the addition of 1.0 ml (5.0 mmol) ofdiethyl phthalate, the mixture was reacted for 1 hour with stirringunder reflux. The resulting reaction mixture was allowed to stand, andthe supernatant liquid was removed to obtain a reaction product slurry.

After the addition of 150 ml of n-heptane (60° C.) to the reactionproduct slurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated seven timesto wash the reaction product, followed by drying under reduced pressureto obtain a powdery solid catalyst component (A10) for olefinpolymerization.

The solid catalyst component (A10) had a magnesium atom content of 18.9mass %, a titanium atom content of 1.8 mass %, a halogen atom content of63.6 mass %, and a total phthalic diester content of 15.4 mass %.

Preparation of Polymerization Catalyst and Polymerization of Propylene

A polymerization catalyst was prepared, and propylene was polymerized inthe same manner as in Example 1, except that the solid catalystcomponent (A10) was used instead of the solid catalyst component (A1),0.13 mmol of diethylaminotriethoxysilane (DEATES) was used instead of0.13 mmol of dicyclopentyldimethoxysilane (DCPDMS), and the amount ofhydrogen gas was changed from 9.0 l to 6.0 l, and the polymerizationactivity and the resulting polymer were evaluated. The results are shownin Table 2.

Comparative Example 1 Synthesis of Solid Catalyst Component

A solid catalyst component was produced as described below withoutperforming the third step.

(1) First Reaction Step

A 500 ml round bottom flask equipped with a stirrer in which theinternal atmosphere had been sufficiently replaced by nitrogen gas, wascharged with 20 ml (182 mmol) of titanium tetrachloride and 40 ml (376mmol) of toluene to prepare a solution.

A suspension prepared using 10 g (88 mmol) of sphericaldiethoxymagnesium (sphericity (l/w): 1.10) and 47 ml (442 mmol) oftoluene was added to the solution. The mixture was stirred at 4° C. for1 hour. After the addition of 2.7 ml (10.2 mmol) of di-n-butylphthalate, the mixture was heated to 105° C., and reacted for 2 hourswith stirring. The resulting reaction mixture was allowed to stand, andthe supernatant liquid was removed to obtain a reaction product slurry.

After the addition of 87 ml of toluene (100° C.) to the reaction productslurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated four timesto wash the reaction product. After the addition of 20 ml of titaniumtetrachloride and 80 ml of toluene, the mixture was heated to 100° C.,and reacted for 2 hours with stirring. The resulting reaction mixturewas allowed to stand, and the supernatant liquid was removed to obtain areaction product slurry.

After the addition of 87 ml of toluene (100° C.) to the reaction productslurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated four timesto wash the reaction product to obtain a reaction product slurryincluding a solid component.

(2) Second Reaction Step

20 ml (182 mmol) of titanium tetrachloride, 47 ml (442 mmol) of toluene,and 0.54 ml (2.0 mmol) of di-n-butyl phthalate were added to thereaction product slurry including the solid component. The mixture washeated to 100° C., and reacted for 2 hours with stirring. The resultingreaction mixture was allowed to stand, and the supernatant liquid wasremoved to obtain a reaction product slurry.

After the addition of 87 ml of toluene (100° C.) to the reaction productslurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated four times.After the addition of 67 ml of n-heptane (40° C.), the mixture wasstirred and allowed to stand, and the supernatant liquid was removed.This operation was repeated ten times to wash the reaction product toobtain a solid catalyst component (a1) in the form of a slurry.

The solid catalyst component (a1) had a magnesium atom content of 18.8mass %, a titanium atom content of 1.9 mass %, a halogen atom content of64.0 mass %, and a total phthalic diester content of 14.9 mass %.

Preparation of Polymerization Catalyst and Polymerization of Propylene

A polymerization catalyst was prepared, and propylene was polymerized inthe same manner as in Example 1, except that the solid catalystcomponent (a1) was used instead of the solid catalyst component (A1),and the polymerization activity and the resulting polymer wereevaluated. The results are shown in Table 2.

Comparative Example 2

A solid catalyst component (a2) was produced in the same manner as inComparative Example 1, except that 3.3 ml (13.4 mmol) of dimethyldiisobutylmalonate was used in the second reaction step (see (2))instead of 0.54 ml of di-n-butyl phthalate.

The solid catalyst component (a2) had a magnesium atom content of 18.6mass %, a titanium atom content of 1.5 mass %, a halogen atom content of64.9 mass %, and a total content of the phthalic diester and thediisobutylmalonic diester of 13.8 mass %.

A polymerization catalyst was prepared, and propylene was polymerized inthe same manner as in Example 1, except that the solid catalystcomponent (a2) was used instead of the solid catalyst component (A1),and the polymerization activity and the resulting polymer wereevaluated. The results are shown in Table 2.

Comparative Example 3

A solid catalyst component (a2) was produced in the same manner as inComparative Example 2. A polymerization catalyst was prepared, andpropylene was polymerized in the same manner as in Comparative Example2, except that 0.13 mmol of dicyclopentylbis(ethylamino)silane (DCPEAS)was used instead of 0.13 mmol of dicyclopentyldimethoxysilane (DCPDMS),and the amount of hydrogen gas was changed from 9.0 l to 6.0 l, and thepolymerization activity and the resulting polymer were evaluated. Theresults are shown in Table 2.

TABLE 2 Polymerization activity MFR XS FM NMR-mmmm (g-pp/g-cat) (g/10min) (mass %) Mw/Mn (MPa) (%) Example 1 71,300 25 0.5 4.6 1710 98.2Example 2 70,600 23 0.5 4.4 1750 98.6 Example 3 61,100 140 0.7 4.6 181098.5 Example 4 48,000 180 0.8 4.5 1820 98.3 Example 5 49,200 200 0.7 3.81800 98.6 Example 6 50,500 140 0.7 3.9 1760 98.0 Example 7 74,100 23 0.64.7 1720 98.5 Example 8 69,900 29 0.6 4.8 1790 98.5 Example 9 65,800 690.6 4.7 1860 98.4 Example 10 60,100 93 0.8 4.6 1880 98.3 Example 1158,000 56 0.8 4.9 1810 98.1 Example 12 56,200 53 0.8 5.1 1800 98.2Example 13 55,000 46 0.7 4.7 1830 98.2 Example 14 45,300 140 0.9 4.71800 98.1 Comparative 57,600 29 0.9 4.4 1630 97.7 Example 1 Comparative63,100 46 0.9 5.1 1650 97.6 Example 2 Comparative 37,100 170 1.1 4.41630 97.5 Example 3

As is clear from the results shown in Table 2, the olefin polymerizationcatalysts respectively prepared using the solid catalyst componentsobtained in Examples 1 to 14 achieved high olefin polymerizationactivity and good hydrogen response during polymerization, and theresulting polymers had a satisfactory melt flow rate (MFR) (i.e.,exhibited excellent moldability), had a satisfactory molecular weightdistribution (Mw/Mn), had a satisfactory xylene-soluble content (XS) andisotactic pentad fraction (NMR-mmmm) (i.e., exhibited excellentstereoregularity), and had a satisfactory flexural modulus (FM) (i.e.,exhibited excellent physical strength (e.g., rigidity)).

Since the olefin polymerization catalysts obtained in ComparativeExamples 1 to 3 were prepared using the solid catalyst component thatwas produced without performing the third step, the olefinpolymerization activity was low (Comparative Example 3), and theresulting polymer had an inferior isotactic pentad fraction (NMR-mmmm)(i.e., exhibited low stereoregularity) and a low flexural modulus (FM)(Comparative Examples 1 to 3) (see Table 2).

Example 15

A solid catalyst component (A11) was produced in the same manner as inExample 1, except that 0.2 ml (1.4 mmol) of 2-ethoxyethyl methylcarbonate was used in the third step (see (3)) instead of 0.5 ml (2.5mmol) of diethyl phthalate.

The solid catalyst component (A11) had a magnesium atom content of 19.8mass %, a titanium atom content of 1.6 mass %, a halogen atom content of62.6 mass %, a phthalic diester content of 11.6 mass %, and a2-ethoxyethyl methyl carbonate content of 0.9 mass %.

Preparation of Propylene Polymerization Catalyst and Polymerization ofPropylene

An autoclave (internal volume: 2.0 l) equipped with a stirrer in whichthe internal atmosphere had been completely replaced by nitrogen gas,was charged with 1.32 mmol of triethylaluminum, 0.13 mmol ofcyclohexylmethyldimethoxysilane (CMDMS), and the solid catalystcomponent (A11) (0.0013 mmol on a titanium atom basis) to prepare anolefin polymerization catalyst.

The autoclave was charged with 9.0 l of hydrogen gas and 1.4 l ofliquefied propylene. The liquefied propylene was subjected topreliminary polymerization at 20° C. for 5 minutes under a pressure of1.1 MPa, heated, and polymerized at 70° C. for 1 hour under a pressureof 3.5 MPa to obtain a propylene polymer (polypropylene).

The polymerization activity per gram of the solid catalyst component,and the melt flow rate (MFR), the p-xylene-soluble content (XS), and theisotactic pentad fraction (NMR-mmmm) of the resulting polypropylene weremeasured in the same manner as described above. The results are shown inTable 3.

Example 16

A solid catalyst component (A12) was produced in the same manner as inExample 2, except that 0.4 ml (1.7 mmol) of di-n-propyl phthalate wasused in the second step (see (2)) instead of 0.5 ml (2.2 mmol) ofdi-n-propyl phthalate, and 0.4 ml (2.8 mmol) of 2-ethoxyethyl methylcarbonate was used in the third step (see (3)) instead of 0.5 ml (2.5mmol) of diethyl phthalate.

The solid catalyst component (A12) had a magnesium atom content of 20.1mass %, a titanium atom content of 1.5 mass %, a halogen atom content of62.3 mass %, a phthalic diester content of 12.1 mass %, and a2-ethoxyethyl methyl carbonate content of 1.5 mass %.

Preparation of Polymerization Catalyst and Polymerization

A polymerization catalyst was prepared, and propylene was polymerized(i.e., polypropylene was produced) in the same manner as in Example 15,except that the resulting solid catalyst component (A12) was used, andthe propylene polymerization activity and the resulting polymer wereevaluated. The results are shown in Table 3.

Preparation of Copolymerization Catalyst and Ethylene-Propylene BlockCopolymerization

A copolymerization catalyst was prepared as described below using thesolid catalyst component (A12), and a copolymer was produced bymultistep polymerization as described below. The ethylene-propyleneblock copolymerization activity (ICP (impact copolymer) activity) duringcopolymerization was measured to evaluate the sustainability ofpolymerization activity, and the block ratio, the flexural modulus (FM),and the Izod impact strength of the resulting ethylene-propylene blockcopolymer were measured.

An autoclave (internal volume: 2.0 l) equipped with a stirrer in whichthe internal atmosphere had been completely replaced by nitrogen gas,was charged with 2.4 mmol of triethylaluminum, 0.24 mmol ofcyclohexylmethyldimethoxysilane, and the solid catalyst component (A12)(0.003 mmol on a titanium atom basis) to prepare an ethylene-propylenecopolymerization catalyst (B12).

An autoclave equipped with a stirrer was charged with 10.2 mg of theethylene-propylene copolymerization catalyst (B12), and further chargedwith liquefied propylene (15 mol) and hydrogen gas (partial pressure:0.20 MPa). The liquefied propylene was subjected to preliminarypolymerization at 20° C. for 5 minutes, and subjected to first-stephomopropylene polymerization (homopolymerization) at 70° C. for 75minutes. The pressure inside the autoclave was then returned to normalpressure.

After feeding ethylene, propylene, and hydrogen to the autoclave in amolar ratio of 1.0/1.0/0.043, the mixture was heated to 70° C., andreacted at 70° C. for 1 hour under a pressure of 1.2 MPa while feedingethylene, propylene, and hydrogen in a ratio of 2/2/0.086 (l/min) toobtain an ethylene-propylene copolymer.

The flexural modulus (FM) of the ethylene-propylene copolymer wasmeasured in the same manner as described above, and theethylene-propylene block copolymerization activity (ICP activity)(kg-ICP/(g-cat·hr)), the block ratio (mass %), and the Izod impactstrength were measured as described below. The results are shown inTable 4.

Ethylene-Propylene Block Copolymerization Activity (ICP Activity)(Kg-ICP/(g-Cat·Hr))

The ethylene-propylene block copolymerization activity (ICP activity)when producing the ethylene-propylene block copolymer was calculatedusing the following expression.

Ethylene-propylene block copolymerization activity(kg-ICP/(g-cat·hr))=((I (kg)−G (kg))/(mass (g) of solid catalystcomponent included in olefin polymerization catalyst)×1.0 (hr))

Note that I is the mass (kg) of the autoclave after completion ofcopolymerization, G is the mass (kg) of the autoclave after unreactedmonomers had been removed after completion of homo-PP polymerization.

Block Ratio (Mass %)

The block ratio of the copolymer was calculated using the followingexpression.

Block ratio (mass %)={(I (g)−G (g))/(I (g)−F (g))}×100

Note that I is the mass (g) of the autoclave after completion ofcopolymerization, G is the mass (g) of the autoclave after unreactedmonomers had been removed after completion of homo-PP polymerization,and F is the mass (g) of the autoclave.

Izod Impact Strength

0.10 wt % of IRGANOX 1010 (manufactured by BASF), 0.10 wt % of IRGAFOS168 (manufactured by BASF), and 0.08 wt % of calcium stearate were addedto the ethylene-propylene copolymer, and the mixture was kneaded andgranulated using a single-screw extruder to obtain pellets of theethylene-propylene copolymer.

The pellets of the ethylene-propylene copolymer were introduced into aninjection molding machine (mold temperature: 60° C., cylindertemperature: 230° C.), and injection-molded to prepare a propertymeasurement specimen.

The specimen was conditioned in a temperature-controlled room maintainedat 23° C. for 144 hours or more, and the Izod impact strength (23° C.and −30° C.) of the specimen was measured in accordance with JIS K 7110(“Method of Izod Impact Test For Rigid Plastics”) using an Izod tester(“Model A-121804405” manufactured by Toyo Seiki Seisaku-Sho, Ltd.).

Shape of specimen: ISO 180/4A, thickness: 3.2 mm, width: 12.7 mm,length: 63.5 mmShape of notch: type-A notch (radius: 0.25 mm) formed using a dieprovided with a notch

Temperature: 23° C. and −30° C.

Impact speed: 3.5 m/sNominal pendulum energy: 5.5 J (23° C.) and 2.75 J (−30° C.)

Example 17

A propylene polymerization catalyst and an ethylene-propylenecopolymerization catalyst were prepared in the same manner as in Example16 using the solid catalyst component (A12) obtained in Example 16,except that 0.13 mmol or 0.24 mmol of dicyclopentyldimethoxysilane(DCPDMS) was used instead of 0.13 mmol or 0.24 mmol ofcyclohexylmethyldimethoxysilane (CMDMS), and polypropylene and anethylene-propylene block copolymer were produced. The propylenepolymerization activity, the ethylene-propylene block copolymerizationactivity (ICP activity), and the resulting polymers were evaluated. Theresults are shown in Tables 3 and 4.

Example 18

A propylene polymerization catalyst and an ethylene-propylenecopolymerization catalyst were prepared in the same manner as in Example16 using the solid catalyst component (A12) obtained in Example 16,except that 0.13 mmol or 0.24 mmol of diisopropyldimethoxysilane(DIPDMS) was used instead of 0.13 mmol or 0.24 mmol ofcyclohexylmethyldimethoxysilane (CMDMS), and polypropylene and anethylene-propylene block copolymer were produced. The propylenepolymerization activity, the ethylene-propylene block copolymerizationactivity (ICP activity), and the resulting polymers were evaluated inthe same manner as described above. The results are shown in Tables 3and 4.

Example 19

A propylene polymerization catalyst and an ethylene-propylenecopolymerization catalyst were prepared in the same manner as in Example16 using the solid catalyst component (A12) obtained in Example 16,except that 0.13 mmol or 0.24 mmol of dicyclopentylbis(ethylamino)silane(DCPEAS) was used instead of 0.13 mmol or 0.24 mmol ofcyclohexylmethyldimethoxysilane (CMDMS), and polypropylene and anethylene-propylene block copolymer were produced. The propylenepolymerization activity, the ethylene-propylene block copolymerizationactivity (ICP activity), and the resulting polymers were evaluated inthe same manner as described above. The results are shown in Tables 3and 4.

Example 20

A propylene polymerization catalyst and an ethylene-propylenecopolymerization catalyst were prepared in the same manner as in Example15 using the solid catalyst component (A12) obtained in Example 16,except that 0.13 mmol or 0.24 mmol of diethylaminotriethoxysilane(DEATES) was used instead of 0.13 mmol or 0.24 mmol ofcyclohexylmethyldimethoxysilane (CMDMS), and polypropylene and anethylene-propylene block copolymer were produced in the same manner asin Example 16, except that the amount of hydrogen gas fed duringpropylene homopolymerization was changed from 9.0 l to 6.0 l. Thepropylene polymerization activity, the ethylene-propylene blockcopolymerization activity (ICP activity), and the resulting polymerswere evaluated in the same manner as described above. The results areshown in Tables 3 and 4.

Example 21

A propylene polymerization catalyst and an ethylene-propylenecopolymerization catalyst were prepared in the same manner as in Example16 using the solid catalyst component (A12) obtained in Example 16,except that 0.13 mmol or 0.24 mmol of a mixture prepared by mixingdicyclopentyldimethoxysilane and n-propyltriethoxysilane in a ratio of5:95 (mol/mol) was used instead of 0.13 mmol or 0.24 mmol ofcyclohexylmethyldimethoxysilane (CMDMS), and polypropylene and anethylene-propylene block copolymer were produced. The propylenepolymerization activity, the ethylene-propylene block copolymerizationactivity (ICP activity), and the resulting polymers were evaluated inthe same manner as described above. The results are shown in Tables 3and 4.

Example 22

A solid catalyst component (A13) was produced in the same manner as inExample 16, except that 0.2 ml (1.4 mmol) of 2-ethoxyethyl methylcarbonate was used in the second step (see (2)) instead of 0.4 ml (1.7mmol) of di-n-propyl phthalate.

The solid catalyst component (A13) had a magnesium atom content of 20.6mass %, a titanium atom content of 1.1 mass %, a halogen atom content of63.0 mass %, a phthalic diester content of 12.7 mass %, and a2-ethoxyethyl methyl carbonate content of 2.3 mass %.

A propylene polymerization catalyst was prepared, and polypropylene wasproduced in the same manner as in Example 15, except that the solidcatalyst component (A13) was used instead of the solid catalystcomponent (A11), and the propylene polymerization activity and theresulting polymer were evaluated. The results are shown in Table 3.

Example 23

A solid catalyst component (A14) was produced in the same manner as inExample 16, except that 0.4 ml (2.5 mmol) of 2-ethoxyethyl ethylcarbonate was used in the third step (see (3)) instead of 0.4 ml (2.8mmol) of 2-ethoxyethyl methyl carbonate.

The solid catalyst component (A14) had a magnesium atom content of 19.5mass %, a titanium atom content of 1.4 mass %, a halogen atom content of61.3 mass %, a total internal electron donor compound content of 15.5mass %, and a 2-ethoxyethyl ethyl carbonate content of 1.6 mass %.

A propylene polymerization catalyst was prepared, and polypropylene wasproduced in the same manner as in Example 15, except that the solidcatalyst component (A14) was used instead of the solid catalystcomponent (A11), and the propylene polymerization activity and theresulting polymer were evaluated. The results are shown in Table 3.

Example 24

A solid catalyst component (A15) was produced in the same manner as inExample 16, except that 0.4 ml (2.1 mmol) of 2-ethoxyethyl phenylcarbonate was used in the third step (see (3)) instead of 0.4 ml (2.8mmol) of 2-ethoxyethyl methyl carbonate.

The solid catalyst component (A14) had a magnesium atom content of 20.1mass %, a titanium atom content of 1.4 mass %, a halogen atom content of61.8 mass %, a total phthalic diester content of 13.0 mass %, and a2-ethoxyethyl phenyl carbonate content of 1.1 mass %.

A propylene polymerization catalyst was prepared, and polypropylene wasproduced in the same manner as in Example 15, except that the solidcatalyst component (A15) was used instead of the solid catalystcomponent (A11), and the propylene polymerization activity and theresulting polymer were evaluated. The results are shown in Table 3.

Example 25

A solid catalyst component (A16) was produced in the same manner as inExample 16, except that 0.4 ml (1.6 mmol) of3,3-bis(methoxymethyl)-2,6-dimethylheptane was used in the second step(see (2)) instead of 0.4 ml (1.7 mmol) of di-n-propyl phthalate, and0.35 ml (1.4 mmol) of 3,3-bis(methoxymethyl)-2,6-dimethylheptane wasused in the third step (see (3)) instead of 0.4 ml (2.8 mmol) of2-ethoxyethyl methyl carbonate.

The solid catalyst component (A16) had a magnesium atom content of 18.9mass %, a titanium atom content of 1.3 mass %, a halogen atom content of59.2 mass %, and a total internal electron donor compound content of16.5 mass %.

A propylene polymerization catalyst was prepared, and polypropylene wasproduced in the same manner as in Example 15, except that the solidcatalyst component (A16) was used instead of the solid catalystcomponent (A11), and the propylene polymerization activity and theresulting polymer were evaluated. The results are shown in Table 3.

Example 26

A solid catalyst component (A17) was produced in the same manner as inExample 16, except that 0.4 ml (1.6 mmol) of9,9-bis(methoxymethyl)fluorene was used in the second step (see (2))instead of 0.4 ml (1.7 mmol) of di-n-propyl phthalate, and 0.4 g (1.6mmol) of 9,9-bis(methoxymethyl)fluorene was used in the third step (see(3)) instead of 0.4 ml (2.8 mmol) of 2-ethoxyethyl methyl carbonate.

The solid catalyst component (A17) had a magnesium atom content of 18.8mass %, a titanium atom content of 1.4 mass %, a halogen atom content of60.5 mass %, and a total internal electron donor compound content of16.6 mass %.

A propylene polymerization catalyst was prepared, and polypropylene wasproduced in the same manner as in Example 15, except that the solidcatalyst component (A17) was used instead of the solid catalystcomponent (A11), and the propylene polymerization activity and theresulting polymer were evaluated. The results are shown in Table 3.

Example 27 Production of Solid Catalyst Component (1) First Step

A 500 ml round-bottom flask equipped with a stirrer in which theinternal atmosphere had been sufficiently replaced by nitrogen gas, wascharged with 120 ml (819 mmol) of n-heptane. After the addition of 15 g(158 mmol) of anhydrous magnesium chloride and 106 ml (274 mmol) oftetrabutoxytitanium, the mixture was reacted at 90° C. for 1.5 hours toobtain a homogenous solution. After cooling the solution to 40° C., 24ml (88 mmol) of methyl hydrogen polysiloxane (20 cSt) was added to thesolution, and a precipitation reaction was effected for 5 hours. Theresulting reaction mixture was allowed to stand, the supernatant liquidwas removed to obtain a reaction product slurry, and the reactionproduct was sufficiently washed with n-heptane.

A 500 ml round-bottom flask equipped with a stirrer in which theinternal atmosphere had been sufficiently replaced by nitrogen gas, wascharged with 40 g of the reaction product, and n-heptane was added tothe flask so that the concentration of the reaction product was 200mg/ml. After the addition of 12 ml (105 mmol) of SiCl₄, the mixture wasreacted at 90° C. for 3 hours. The resulting reaction mixture wasallowed to stand, the supernatant liquid was removed to obtain areaction product slurry, and the reaction product was sufficientlywashed with n-heptane.

After that addition of n-heptane so that the concentration of thereaction product was 100 mg/ml, 20 ml (182 mmol) of TiCl₄ was added tothe mixture. After the addition of 7.2 ml (27.1 mmol) of dibutylphthalate, the mixture was reacted at 95° C. for 3 hours. The resultingreaction mixture was allowed to stand, and the supernatant liquid wasremoved to obtain a reaction product slurry.

After the addition of 120 ml of n-heptane to the reaction productslurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated seven timesto wash the reaction product to obtain a slurry-like intermediatecomposition (1).

(2) Second Step

100 ml (683 mmol) of n-heptane and 20 ml (182 mmol) of titaniumtetrachloride were added to the slurry-like intermediate composition(1). The mixture was heated to 100° C., and reacted for 2 hours withstirring. After completion of the reaction, the supernatant liquid(toluene) was removed, followed by the addition of 100 ml of n-heptane.After the addition of 20 ml of titanium tetrachloride, 0.8 ml (3.4 mmol)of di-n-propyl phthalate was added to the mixture, and the mixture wasreacted at 95° C. for 3 hours. The resulting reaction mixture wasallowed to stand, and the supernatant liquid was removed to obtain areaction product slurry.

After treating the reaction product slurry with 100 ml of heptane underreflux, the mixture was allowed to stand, and the supernatant liquid wasremoved. This operation was repeated twice to wash the reaction productto obtain a slurry-like intermediate composition (2).

(3) Third Step

187 ml (1760 mmol) of toluene was added to the slurry-like intermediatecomposition (2) to adjust the concentration of titanium tetrachloride inthe reaction mixture to 2.5 mass %, and the mixture was heated to 80° C.After the addition of 0.8 ml (5.6 mmol) of 2-ethoxyethyl methylcarbonate, the mixture was reacted for 1 hour with stirring underreflux. The resulting reaction mixture was allowed to stand, and thesupernatant liquid was removed to obtain a reaction product slurry.

After the addition of 150 ml of n-heptane (60° C.) to the reactionproduct slurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated seven timesto wash the reaction product, followed by drying under reduced pressureto obtain a powdery solid catalyst component (A18) for olefinpolymerization.

The solid catalyst component (A18) had a magnesium atom content of 19.6mass %, a titanium atom content of 1.8 mass %, a halogen atom content of62.6 mass %, a total content of the phthalic diester and the ethercompound of 13.1 mass %, and a 2-ethoxyethyl methyl carbonate content of1.1 mass %.

Preparation of Polymerization Catalyst and Polymerization

A propylene polymerization catalyst was prepared, and polypropylene wasproduced in the same manner as in Example 15, except that the solidcatalyst component (A18) was used instead of the solid catalystcomponent (A11), 0.13 mmol of diethylaminotriethoxysilane (DEATES) wasused instead of 0.13 mmol of dicyclopentyldimethoxysilane (DCPDMS), andthe amount of hydrogen gas was changed from 9.0 l to 6.0 l, and thepropylene polymerization activity and the resulting polymer wereevaluated. The results are shown in Table 3.

Example 28 Production of Solid Catalyst Component

A solid catalyst component (A19) was produced in the same manner as inExample 16, except that 0.4 ml (1.6 mmol) of3,3-bis(methoxymethyl)-2,6-dimethylheptane was used in the third step(see (3)) instead of 0.4 ml (2.8 mmol) of 2-ethoxyethyl methylcarbonate.

The solid catalyst component (A19) had a magnesium atom content of 19.2mass %, a titanium atom content of 1.3 mass %, a halogen atom content of60.0 mass %, a total content of the phthalic diester and the ethercompound of 14.6 mass %, and a3,3-bis(methoxymethyl)-2,6-dimethylheptane content of 1.6 mass %.

Preparation of Polymerization Catalyst and Polymerization

A propylene polymerization catalyst was prepared, and polypropylene wasproduced in the same manner as in Example 15, except that the solidcatalyst component (A19) was used instead of the solid catalystcomponent (A11), and the propylene polymerization activity and theresulting polymer were evaluated. The results are shown in Table 3.

Comparative Example 4

A solid catalyst component was produced as described below withoutperforming the third step.

Synthesis of Solid Catalyst Component (1) First Reaction Step

A 500 ml round bottom flask equipped with a stirrer in which theinternal atmosphere had been sufficiently replaced by nitrogen gas, wascharged with 20 ml (182 mmol) of titanium tetrachloride and 40 ml (376mmol) of toluene to prepare a solution.

A suspension prepared using 10 g (88 mmol) of sphericaldiethoxymagnesium (sphericity (l/w): 1.10) and 47 ml (442 mmol) oftoluene was added to the solution. The mixture was stirred at 4° C. for1 hour. After the addition of 2.4 ml (10.3 mmol) of di-n-propylphthalate, the mixture was heated to 105° C., and reacted for 2 hourswith stirring. The resulting reaction mixture was allowed to stand, andthe supernatant liquid was removed to obtain a reaction product slurry.

After the addition of 87 ml of toluene (100° C.) to the reaction productslurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated four timesto wash the reaction product. After the addition of 20 ml of titaniumtetrachloride and 80 ml of toluene, the mixture was reacted for 2 hourswith stirring. The resulting reaction mixture was allowed to stand, andthe supernatant liquid was removed to obtain a reaction product slurry.

After the addition of 87 ml of toluene (100° C.) to the reaction productslurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated four timesto wash the reaction product to obtain a reaction product slurryincluding a solid component.

(2) Second Reaction Step

20 ml (182 mmol) of titanium tetrachloride, 47 ml (442 mmol) of toluene,and 0.2 ml (0.8 mmol) of 3,3-bis(methoxymethyl)-2,6-dimethylheptane wereadded to the reaction product slurry including the solid component. Themixture was heated to 100° C., and reacted for 2 hours with stirring.The resulting reaction mixture was allowed to stand, and the supernatantliquid was removed to obtain a reaction product slurry. After theaddition of 87 ml of toluene (100° C.) to the reaction product slurry,the mixture was stirred and allowed to stand, and the supernatant liquidwas removed. This operation was repeated four times. After the additionof 67 ml of n-heptane (40° C.), the mixture was stirred and allowed tostand, and the supernatant liquid was removed. This operation wasrepeated ten times to wash the reaction product to obtain a solidcatalyst component (a4) in the form of a slurry.

The solid catalyst component (a4) had a magnesium atom content of 19.5mass %, a titanium atom content of 2.2 mass %, a halogen atom content of62.9 mass %, a total internal electron donor compound content of 14.6mass %, and a 3,3-bis(methoxymethyl)-2,6-dimethylheptane content of 1.8mass %.

Preparation of Polymerization Catalyst and Polymerization

A propylene polymerization catalyst was prepared, and polypropylene wasproduced in the same manner as in Example 15, except that the solidcatalyst component (a4) was used instead of the solid catalyst component(A11), and the propylene polymerization activity and the resultingpolymer were evaluated. The results are shown in Table 3.

Example 29 Preparation of Polymerization Catalyst and Polymerization

An ethylene-propylene copolymerization catalyst was prepared, and anethylene-propylene block copolymer was produced in the same manner as inExample 16, except that the solid catalyst component (A2) was usedinstead of the solid catalyst component (A11), and theethylene-propylene block copolymerization activity (ICP activity) andthe resulting polymer were evaluated. The results are shown in Table 4.

Example 30

An ethylene-propylene copolymerization catalyst was prepared, and anethylene-propylene block copolymer was produced in the same manner as inExample 29. A propylene-based block copolymer was produced by furtherpolymerization at 70° C. for 0.5 hours under a pressure of 1.2 MPa whilefeeding ethylene, propylene, and hydrogen in a ratio of 2.0/1.0/0.043(l/min), and the ethylene-propylene block copolymerization activity (ICPactivity) and the resulting polymer were evaluated in the same manner asdescribed above. The results are shown in Table 4.

Example 31

An ethylene-propylene copolymerization catalyst was prepared, and anethylene-propylene block copolymer was produced in the same manner as inExample 29. After returning the pressure inside the autoclave to normalpressure, and adding 10 g of l-butene, ethylene, propylene, and hydrogenwere fed to the autoclave in a molar ratio of 2.0/1.0/0.043, and apropylene-based block copolymer was produced by further polymerizationat 70° C. for 0.5 hours under a pressure of 1.2 MPa while feedingethylene, propylene, and hydrogen in a ratio of 2.0/1.0/0.043 (l/min(flow rate)), and the ethylene-propylene block copolymerization activity(ICP activity) and the resulting polymer were evaluated in the samemanner as described above. The results are shown in Table 4.

Comparative Example 5 Preparation of Polymerization Catalyst andPolymerization

An ethylene-propylene copolymerization catalyst was prepared, and anethylene-propylene block copolymer was produced in the same manner as inExample 15, except that the solid catalyst component (a1) was usedinstead of the solid catalyst component (A11), and theethylene-propylene block copolymerization activity (ICP activity) andthe resulting polymer were evaluated. The results are shown in Table 4.

TABLE 3 Polymerization NMR- activity MFR XS mmmm FM (g-pp/g-cat) (g/10min) (mass %) (%) (MPa) Example 15 64,300 22 0.6 98.5 1770 Example 1661,500 20 0.4 99.1 1810 Example 17 58,200 58 0.8 98.2 1750 Example 1860,100 110 0.5 98.8 1880 Example 19 55,400 200 0.7 98.7 1870 Example 2056,100 220 0.7 98.8 1870 Example 21 58,600 140 0.8 98.5 1850 Example 2249,000 19 0.7 98.8 1880 Example 23 56,500 18 0.7 98.6 — Example 2449,500 17 0.8 98.5 — Example 25 60,700 25 0.6 98.4 — Example 26 58,50023 0.6 98.3 — Example 27 48,700 21 0.9 98.3 1800 Example 28 57,900 170.6 98.4 — Comparative 54,500 22 1.3 97.5 — Example 4

TABLE 4 ICP polymerization Izod impact strength Izod impact strengthactivity Block ratio FM (23° C.) (−30° C.) (kg-ICP/g-cat · hr) (mass %)(MPa) (J/m) (J/m) Example 16 17.3 27 1150 Did not break 7.6 Example 1715.6 25 1210 Did not break 7.0 Example 18 16.2 23 1250 16.3 6.5 Example19 17.5 32 1030 Did not break 9.2 Example 20 14.5 21 1400 10.0 4.5Example 21 15.0 23 1300 12.5 6.0 Example 29 14.0 24 1280 12.4 5.9Example 30 19.0 33 1050 Did not break 9.5 Example 31 18.8 32 1100 Didnot break 9.9 Comparative 11.3 20 1050  8.5 4.9 Example 5

As is clear from the results shown in Tables 3 and 4, the olefinpolymerization catalysts respectively prepared using the solid catalystcomponents obtained in Examples 15 to 31 achieved high olefinpolymerization activity, and achieved high ICP polymerization activity(i.e., exhibited high sustainability of olefin polymerization duringcopolymerization), and the resulting propylene polymers had asatisfactory melt flow rate (MFR) (i.e., exhibited excellentmoldability), and had a satisfactory xylene-soluble content (XS) andisotactic pentad fraction (NMR-mmmm) (i.e., exhibited excellentstereoregularity), and the resulting copolymers had a satisfactory blockratio (i.e., excellent impact copolymer (ICP) copolymerizationperformance was achieved). The balance between rigidity and impactresistance was also improved.

Since the olefin polymerization catalyst obtained in Comparative Example4 was prepared using the solid catalyst component that was producedwithout performing the third step, the resulting propylene polymer had alow xylene-soluble content (XS) and a low isotactic pentad fraction(NMR-mmmm) (i.e., exhibited inferior stereoregularity) (see Table 3).

Since the olefin polymerization catalyst obtained in Comparative Example5 was prepared using the solid catalyst component that was producedwithout performing the third step, the olefin polymerization catalystachieved low ICP polymerization activity (i.e., exhibited inferiorsustainability of olefin polymerization during copolymerization), andproduced a copolymer having a low block ratio (i.e., achieved lowcopolymerization activity), and the resulting copolymer had a lowflexural modulus (FM) and a low Izod impact strength (i.e., hadinsufficient rigidity) (see Table 4).

INDUSTRIAL APPLICABILITY

The embodiments of the invention thus provide a method for producing anovel solid catalyst component for olefin polymerization that achievesexcellent olefin polymerization activity and activity with respect tohydrogen during polymerization when homopolymerizing or copolymerizingan olefin, and can produce an olefin polymer that exhibits a high MFR,high stereoregularity, and excellent rigidity while achieving highsustainability of polymerization activity, and also provide an olefinpolymerization catalyst and a method for producing an olefin polymer.

1. A method for producing a solid catalyst component for olefinpolymerization, the method comprising: bringing a magnesium compound, atetravalent titanium halide compound, and one or more first internalelectron donor compounds which are aromatic dicarboxylic diesters offormula (I) into contact with each other to effect a reaction, followedby washing, thereby obtaining a first product; bringing a tetravalenttitanium halide compound and one or more second internal electron donorcompounds into contact with the first product to effect a reaction,followed by washing, thereby obtaining a second product; and bringingone or more third internal electron donor compounds into contact withthe second product to effect a reaction,(R¹)_(j)C₆H_(4-j)(COOR²)(COOR³)  (I) wherein R¹ is independently analkyl group having comprising 1 to 8 carbon atoms or a halogen atom, R²and R³ are each independently an alkyl group comprising 1 to 12 carbonatoms, and j is a number of 0, 1, or
 2. 2. The method according to claim1, wherein a molar ratio of the second internal electron donor compoundto the magnesium compound is 0.001 to
 10. 3. The method according toclaim 1, wherein a molar ratio of the third internal electron donorcompound to the magnesium compound is 0.001 to
 10. 4. The methodaccording to claim 1, wherein a molar quantity of the first internalelectron donor compound is larger than a molar quantity of the secondinternal electron donor compound, which is larger than or equal to amolar quantity of the third internal electron donor compound.
 5. Themethod according to claim 1, wherein the third internal electron donorcompound is brought into contact with the second product in an inertorganic solvent for which a tetravalent titanium halide compound contentis controlled to 0 to 5 mass %.
 6. An olefin polymerization catalystobtained by a process comprising: bringing a solid catalyst componentfor olefin polymerization obtained by the method according to claim 1,an organoaluminum compound of formula (II), and an external electrondonor compound into contact with each other,R⁴ _(p)AlQ_(3-p)  (II) wherein R⁴ is an alkyl group comprising 1 to 6carbon atoms, Q is a hydrogen atom or a halogen atom, and p is a realnumber that satisfies 0<p≦3.
 7. The olefin polymerization catalystaccording to claim 6, wherein the external electron donor compound isone or more organosilicon compounds selected from the group consistingof an organosilicon compound of formula (III) and an organosiliconcompound of formula (IV),R⁵ _(q)Si(OR⁶)_(4-q)  (III) wherein R⁵ is independently an alkyl groupcomprising 1 to 12 carbon atoms, a cycloalkyl group comprising 3 to 12carbon atoms, a phenyl group, a vinyl group, an allyl group, or anaralkyl group, R⁶ is independently an alkyl group comprising 1 to 4carbon atoms, a cycloalkyl group comprising 3 to 6 carbon atoms, aphenyl group, a vinyl group, an allyl group, or an aralkyl group, and qis an integer of from 0 to 3,(R⁷R⁸N)_(s)SiR⁹ _(4-s)  (IV) wherein R⁷ and R⁸ are independently ahydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, abranched alkyl group comprising 3 to 20 carbon atoms, a vinyl group, anallyl group, an aralkyl group, a cycloalkyl group comprising 3 to 20carbon atoms, or an aryl group, provided that R⁷ and R⁸ optionally bondto each other to form a ring, R⁹ is independently a linear alkyl grouphaving comprising 1 to 20 carbon atoms, a branched alkyl groupcomprising 3 to 20 carbon atoms, a vinyl group, an allyl group, anaralkyl group, a linear or branched alkoxy group comprising 1 to 20carbon atoms, a vinyloxy group, an allyloxy group, a cycloalkyl groupcomprising 3 to 20 carbon atoms, an aryl group, or an aryloxy group, ands is an integer of from 1 to
 3. 8. A method for producing an olefinpolymer, the method comprising polymerizing an olefin in the presence ofthe olefin polymerization catalyst according to claim 6.